Decorative sheet and decorative material

Abstract

A decorative sheet is provided with a colored base material layer and a transparent thermoplastic resin layer laminated on one surface of the colored base material layer, and the colored base material layer contains a biomass-derived polyolefin and has a density in the range of 0.92 g / cm3 to 1.12 g / cm3. The invention also provides a decorative material comprising the decorative sheet.

Description

[0001] This patent application is a divisional application of the patent application with application number 2022800234295, application date March 7, 2022, and invention title "Decorative Piece and Decorative Material". Technical Field

[0002] This invention relates to decorative sheets and decorative materials. Background Technology

[0003] As a substitute for decorative sheets made of polyvinyl chloride, decorative sheets using olefin-based resins have been proposed, for example, as disclosed in Patent Document 1.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2014-188941 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] In recent years, driven by environmental concerns, there has been a demand to replace petroleum-based materials with plant-based materials in decorative panels. However, when biomass polyethylene is used as a plant-based material for decorative panels, a decrease in surface hardness arises.

[0009] In view of the above problems, the object of the present invention is to provide decorative sheets and decorative materials that can suppress the reduction of surface hardness even when formed using materials derived from plants.

[0010] Methods for solving problems

[0011] To address the aforementioned issues, one aspect of the present invention is a decorative sheet comprising: a colored substrate layer and a transparent resin layer laminated on one side of the colored substrate layer, wherein the transparent resin layer is formed using a resin composition containing high-density polyethylene derived from plants, and a nucleating agent is added to the resin composition containing high-density polyethylene.

[0012] In addition, in order to solve the above-mentioned problems, one aspect of the present invention is a decorative material having a substrate and a decorative sheet laminated on at least one side of the substrate.

[0013] The effects of the invention

[0014] According to one aspect of the invention, decorative sheets and decorative materials can be provided that suppress the reduction of surface hardness even when using plant-derived materials, i.e., high-density polyethylene formed from plant materials. Attached Figure Description

[0015] [ Figure 1 [Illustration 1] is a cross-sectional view showing the composition of the decorative sheet and decorative material in the first embodiment of the present invention. Detailed Implementation

[0016] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the drawings, identical or similar parts are labeled with the same or similar symbols, and repeated descriptions are omitted. The drawings are illustrative and may differ from actual embodiments. The embodiments shown below exemplify apparatus or methods for embodying the technical concept of the present invention; the technical concept of the present invention is not specific to the apparatus or methods exemplified in the following embodiments. Various modifications can be made to the technical concept of the present invention within the scope of the claims. Furthermore, the directions "left-right" and "up-down" in the following description are defined merely for ease of explanation and do not limit the technical concept of the present invention. Therefore, for example, if the paper is rotated 90 degrees, "left-right" and "up-down" are read interchangeably; if the paper is rotated 180 degrees, "left" naturally becomes "right," and "right" becomes "left."

[0017] (First Embodiment)

[0018] The following is for reference Figure 1 The composition of decorative material 10 is explained.

[0019] like Figure 1 As shown, the decorative material 10 comprises a decorative piece 1 and a substrate 9. It should be noted that the specific composition of the decorative piece 1 will be described later.

[0020] Substrate 9, for example, is formed into a plate shape using wood-based panels, inorganic panels, metal plates, etc., on one side ( Figure 1 The decorative piece 1 is stacked on one side of the surface (the middle side). That is, the decorative material 10 has a substrate 9 and a decorative piece 1 stacked on one side of the substrate 9.

[0021] (Composition of decorative pieces)

[0022] like Figure 1 As shown, the decorative piece 1 has a colored substrate layer 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer 5, a surface protective layer 6, a raised and recessed portion 7, and a primer layer 8.

[0023] <Colored substrate layer>

[0024] The colored substrate layer 2 is formed using a thermoplastic resin.

[0025] As the thermoplastic resin forming the colored substrate layer 2, for example, a colored thermoplastic polyolefin resin can be used. Examples of polyolefin resins that can be used include: polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, etc.; olefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylate copolymer, ethylene-unsaturated carboxylic acid copolymer metal neutralizer (ionomer), etc., as well as mixtures, copolymers, composites, laminates, etc.

[0026] Furthermore, as a polyolefin resin, it can be appropriately selected and used from the above-mentioned types depending on the intended use of the decorative sheet 1. In particular, polypropylene resins, i.e., homopolymers or copolymers with propylene as the main component, are most suitable for general applications. For example, homopolymers, atactic polypropylene resins, block polypropylene resins, etc., can be used alone or appropriately combined, and resins obtained by further appropriately combining atactic polypropylene can be used. Alternatively, copolymers containing olefin monomers other than propylene can also be used. For example, propylene-α-olefin copolymers, which have a polypropylene crystalline portion and contain 15 mol% or more of α-olefins with 2 to 20 carbon atoms other than propylene, preferably one or more of the comonomers of ethylene, butene-1, 4-methylpentene-1, hexene-1, or octene-1, can be used. In addition, modifiers such as low-density polyethylene, ethylene-α-olefin copolymers, ethylene-propylene copolymer rubbers, ethylene-propylene-nonconjugated diene copolymer rubbers, styrene-butadiene copolymers, or hydrides, which are commonly used to soften polypropylene resins, can be appropriately added.

[0027] Additionally, as needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers may be added to the colored substrate layer 2.

[0028] The thickness of the colored substrate layer 2 is preferably in the range of 40 μm to 150 μm, more preferably 50 μm to 130 μm. This is because when the thickness of the colored substrate layer 2 is 40 μm or more, it can absorb unevenness and steps in the flooring material or the like used as the base, thereby allowing for a smoother installation of the decorative sheet 1. Furthermore, when the thickness of the colored substrate layer 2 is 150 μm or less, a colored substrate layer 2 exceeding the required thickness will not be formed, thus reducing the manufacturing cost of the decorative sheet 1.

[0029] <Pattern Layer>

[0030] Pattern layer 3 is stacked on one side of colored substrate layer 2 (in) Figure 1 On the top side (the middle side), there is a layer for attaching patterns to give the design. It should be noted that if the coloring of the base material layer 2 can be used instead, the pattern layer 3 can also be omitted.

[0031] In addition, the pattern layer 3 is formed using printing inks or coatings. The printing inks or coatings that form the pattern layer 3 are formed, for example, by dissolving or dispersing colorants such as dyes or pigments together with a suitable binder resin in a suitable diluent.

[0032] The printing inks or coatings that form the pattern layer 3 are applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roller coating.

[0033] As an adhesive resin, for example, urethane resins, acrylic resins, vinyl chloroacetate resins, polyimide resins, nitrocellulose, or mixtures thereof can be used, but are not limited thereto.

[0034] As the pattern, any pattern can be used, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, text, symbols, single-color pigments, or combinations thereof. Furthermore, to improve the concealment of the decorative piece 1, a concealing layer can be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer can be formed, for example, using opaque printing inks or coatings containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0035] The thickness of the pattern layer 3 is preferably in the range of 1 μm to 10 μm. This is because when the thickness of the pattern layer 3 is 1 μm or more, the printing becomes clearer. In addition, when the thickness of the pattern layer 3 is 10 μm or less, the printability of the decorative sheet 1 is improved, and manufacturing costs can be reduced.

[0036] In addition, to impart various functions, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesives, desiccants, curing agents, curing accelerators, and curing delayers can be added to pattern layer 3.

[0037] Alternatively, the pattern layer 3 may be configured to have a solid-coated colored substrate layer to conceal the color / pattern of the base of the decorative piece 1, and a pattern layer for attaching a design-specific pattern.

[0038] <Adhesive Layer>

[0039] Adhesive layer 4 is stacked on one side of pattern layer 3 (in) Figure 1On the top side (the middle side), there is a layer used to bond the pattern layer 3 and the transparent resin layer 5.

[0040] Materials used as adhesive layer 4 may include, for example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester-based, and polyolefin-based materials.

[0041] <Transparent resin layer>

[0042] The transparent resin layer 5 is stacked on one side of the adhesive layer 4 (in Figure 1 On the top side (the middle side), a transparent high-density polyethylene derived from plants (e.g., "Green Polyethylene (SHC7260)" manufactured by Braskem) is formed.

[0043] It should be noted that high-density polyethylene derived from plants is, for example, polyethylene with a density exceeding 0.94.

[0044] A nucleating agent (e.g., "Rikemaster CN-002" manufactured by Ricken Vitamin Co., Ltd.) is added to the high-density polyethylene forming the transparent resin layer 5. That is, a nucleating agent is added to the resin composition containing the high-density polyethylene forming the transparent resin layer 5.

[0045] Based on the mass of high-density polyethylene, nucleating agents are added to high-density polyethylene in a range of 500 ppm to 2000 ppm.

[0046] In the first embodiment, as an example, the case where a nucleating agent is added to high-density polyethylene in a range of 1500 ppm to 2000 ppm, based on the mass of the high-density polyethylene, will be described. Furthermore, the density of the transparent resin layer 5 is, for example, 0.92 g / cm³. 3 Above 0.99 g / cm³ 3 Within the range below, preferably 0.94 g / cm³ 3 Above 0.98 g / cm³ 3 Within the range below, more preferably 0.95 g / cm³ 3 Above 0.97 g / cm³ 3 The density within the following range.

[0047] As needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers can be added to the transparent resin layer 5.

[0048] It should be noted that the transparent resin layer 5 preferably has a degree of transparency (colorless transparent, colored transparent, semi-transparent) that allows the pattern of the pattern layer 3 to be seen through the surface (top) of the decorative sheet 1.

[0049] The thickness of the transparent resin layer 5 is, for example, set in the range of 20 [μm] to 200 [μm].

[0050] <Surface Protective Layer>

[0051] Surface protective layer 6 is stacked on one side of transparent resin layer 5 (in) Figure 1 The middle (upper side) is a layer designed to give decorative piece 1 functions such as weather resistance, damage resistance, stain resistance, and design.

[0052] In addition, the surface protective layer 6 is formed, for example, using an acrylic resin composition.

[0053] In addition, depending on the requirements, the surface protective layer 6 may contain various additives such as weather resistant agents, plasticizers, stabilizers, fillers, dispersants, dyes, pigments and other colorants, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst trapping agents, colorants, light scattering agents, and gloss modifiers. Furthermore, depending on the requirements, the surface protective layer 6 may also contain functional additives such as antibacterial agents and antifungal agents.

[0054] <Concave and convex parts>

[0055] The uneven portion 7 is formed by recesses provided at multiple locations in the transparent resin layer 5 and the surface protective layer 6.

[0056] <Primer layer>

[0057] The primer layer 8 is a base layer used to improve the adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9.

[0058] In addition, the primer layer 8 is laminated on the other side of the colored substrate layer 2 (in Figure 1 (The middle is the lower side surface).

[0059] In addition, the primer layer 8 is formed, for example, using polyester resin, organic additives, pigments, etc.

[0060] It should be noted that, in order to improve corrosion resistance, anti-rust pigments can be added to the primer layer 8.

[0061] The thickness of the primer layer 8 is, for example, in the range of 1 [μm] to 10 [μm].

[0062] It should be noted that the first embodiment described above is an example of the present invention. The present invention is not limited to the first embodiment described above. Even in other ways, as long as they do not depart from the technical concept of the present invention, various changes can be made according to the design, etc.

[0063] (Effects of the first embodiment)

[0064] If it is the decorative piece 1 of the first embodiment, it can achieve the effects described below.

[0065] (1) The material comprises a colored substrate layer 2 and a transparent resin layer 5 laminated on one side of the colored substrate layer 2. The transparent resin layer 5 is formed using a resin composition containing high-density polyethylene derived from plants, wherein a nucleating agent is added to the resin composition containing high-density polyethylene. The density of the transparent resin layer 5 is, for example, 0.92 g / cm³. 3 Above 0.99 g / cm³ 3 Within the range below, preferably 0.94 g / cm³ 3 Above 0.98 g / cm³ 3 Within the range below, more preferably 0.95 g / cm³ 3 Above 0.97 g / cm³ 3 The density within the following range.

[0066] Therefore, even when using plant-derived materials, such as high-density polyethylene derived from plants, it is possible to form a transparent resin layer 5 with the same high hardness as that formed using polyethylene derived from fossil fuels.

[0067] As a result, even when using plant-derived materials, i.e., high-density polyethylene formed from plants, decorative sheets 1 can be provided that can suppress the reduction of surface hardness.

[0068] Furthermore, even when using plant-derived materials, such as high-density polyethylene derived from plants, it is possible to form a transparent resin layer 5 with the same high transparency as that formed using polyethylene derived from fossil fuels.

[0069] (2) Nucleating agent is added within the range of 500 ppm to 2000 ppm based on the mass of high-density polyethylene.

[0070] As a result, decorative sheets with less haze can be provided.

[0071] (3) Based on the mass of high-density polyethylene, add nucleating agent in the range of 1500 [ppm] to 2000 [ppm].

[0072] As a result, a decorative sheet with less haze can be provided compared to a composition based on the mass of high-density polyethylene with less than 1500 [ppm] of nucleating agent added.

[0073] In addition, if the decorative material 10 of the first embodiment is used, the following effects can be achieved.

[0074] (4) Having a substrate 9 and a decorative sheet 1 laminated on at least one side of the substrate 9.

[0075] As a result, even when using plant-derived materials, i.e., high-density polyethylene formed from plants, decorative materials 10 can be provided that can suppress the reduction of surface hardness.

[0076] <Modifications of the first embodiment>

[0077] (1) In the first embodiment, the decorative material 10 is configured to have a decorative sheet 1 laminated on one side of the substrate 9, but is not limited thereto. That is, the decorative material 10 may also be configured to have, in addition to having a decorative sheet 1 laminated on one side of the substrate 9, another decorative sheet 1 laminated on the other side of the substrate 9 (in... Figure 1 Decorative piece 1 on the lower side (the middle side).

[0078] Example 1

[0079] Hereinafter, the decorative materials of Examples 1 to 3 and the decorative materials of Comparative Examples 1 and 2 will be described with reference to the first embodiment.

[0080] (Example 1)

[0081] The colored substrate layer is formed using colored polyethylene resin with a thickness of 55 μm.

[0082] The pattern layer is formed using urethane-based printing inks after corona discharge treatment is applied to one side of the colored substrate layer.

[0083] The adhesive layer is formed using maleic anhydride-modified polyethylene resin.

[0084] The transparent resin layer is formed by adding "GreenPolyethylene" manufactured by Braskem, a plant-derived high-density polyethylene (HDPE), as a nucleating agent, "Rikemaster CN-002" manufactured by Riken Vitamin Co., Ltd., at a concentration of 1500 ppm relative to "Green Polyethylene" based on the mass of "Green Polyethylene". The thickness of the transparent resin layer is set to 70 μm.

[0085] The surface protective layer is formed with an acrylic resin composition as the main component.

[0086] The primer layer is made of polyester urethane resin. After corona discharge treatment is performed on one side of the colored substrate layer, the thickness is set to be between 1 μm and 2 μm.

[0087] Then, by performing extrusion lamination, a decorative sheet of Example 1 with a thickness of 135 [μm] was formed.

[0088] After forming the decorative sheet of Example 1, the side of the primer layer opposite to the substrate is adhered to the substrate using "BA-10L (curing agent: BA-11B)" manufactured by Japan Coating Resin Corporation, thereby forming the decorative material of Example 1.

[0089] (Example 2)

[0090] Except for the addition of “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd. as a nucleating agent, which is 500 ppm based on the mass of high-density polyethylene, the decorative sheet and decorative material of Example 2 are formed in the same manner as in Example 1.

[0091] (Example 3)

[0092] Except for the addition of “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd. as a nucleating agent, which is 2000 [ppm] based on the mass of high-density polyethylene, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Example 3.

[0093] (Comparative Example 1)

[0094] Except that no nucleating agent is added to the high-density polyethylene, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Comparative Example 1.

[0095] (Comparative Example 2)

[0096] Except that no nucleating agent is added to the high-density polyethylene and the mixing ratio of high-density polyethylene to low-density polyethylene is 80:20, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Comparative Example 2.

[0097] (Performance evaluation, evaluation results)

[0098] The surface hardness, productivity, transmittance, and haze of the decorative materials of Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated. The methods described below were used as evaluation methods.

[0099] <Surface Hardness>

[0100] After conducting pencil hardness tests on decorative materials using pencils of varying hardness, the surface hardness was evaluated by identifying any damage (dents) on the surface (protective layer). Damage occurring after testing with a pencil with a hardness of 2B or higher was rated as "◎", while damage occurring after testing with a pencil with a hardness of 4B or higher was rated as "○". Furthermore, damage occurring after testing with a pencil with a hardness of 5B or lower was rated as "×".

[0101] Productivity

[0102] Productivity is evaluated based on whether any problems exist in the manufacturing of the decorative sheet. Then, a "◎" is awarded for cases where there are no problems in the manufacturing of the decorative sheet, a "○" is awarded for cases where there are no production problems in the manufacturing of the decorative sheet, and a "×" is awarded for cases where there are problems in the manufacturing of the decorative sheet.

[0103] <Transparency>

[0104] With the thickness of the transparent resin layer set between 70 μm and 80 μm, the total light transmittance at a wavelength of 555 nm was measured using a spectrophotometer (integrating sphere) to evaluate the transmittance. A total light transmittance of 85% was rated as "◎", a total light transmittance between 80% and 85% was rated as "○", and a total light transmittance less than 80% was rated as "×".

[0105] <Haze>

[0106] Using the inventor's specified criteria, the appearance design is evaluated to assess whether there are any obstacles when used as a decorative sheet, thereby evaluating the haze.

[0107]

[0108] The results of evaluating various properties using the above method show that the decorative materials of Examples 1 to 3 exhibited excellent performance in all evaluation tests. On the other hand, the decorative materials of Comparative Examples 1 and 2 did not exhibit excellent performance in all evaluation tests.

[0109] (Second Implementation)

[0110] The following is for reference Figure 1The composition of decorative material 10 is explained.

[0111] like Figure 1 As shown, the decorative material 10 includes a decorative piece 1 and a substrate 9.

[0112] It should be noted that the composition of the decorative material 10 in the second embodiment is the same as that in the first embodiment, except for the composition of the decorative piece 1. Therefore, the description of the composition other than the decorative piece 1 is omitted.

[0113] (Composition of decorative pieces)

[0114] like Figure 1 As shown, the decorative piece 1 has a colored substrate layer 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer 5, a surface protective layer 6, a raised and recessed portion 7, and a primer layer 8.

[0115] <Colored substrate layer>

[0116] The colored substrate layer 2 is formed using a thermoplastic resin.

[0117] As the thermoplastic resin forming the colored substrate layer 2, for example, a colored thermoplastic polyolefin resin can be used. Examples of polyolefin resins that can be used include: polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, etc.; olefin copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylate copolymer, ethylene-unsaturated carboxylic acid copolymer metal neutralizer (ionomer), etc., as well as mixtures, copolymers, composites, laminates, etc.

[0118] Alternatively, the colored substrate layer 2 may also be formed from a resin composition containing high-density polyethylene derived from plants. Furthermore, in addition to containing high-density polyethylene derived from plants, the colored substrate layer 2 may also contain low-density polyethylene derived from plants, or linear low-density polyethylene derived from plants.

[0119] Furthermore, as a polyolefin resin, it can be appropriately selected and used from the above-mentioned types depending on the intended use of the decorative sheet 1. In particular, polypropylene resins, i.e., homopolymers or copolymers with propylene as the main component, are most suitable for general applications. For example, homopolymers, atactic polypropylene resins, block polypropylene resins, etc., can be used alone or appropriately combined, and resins obtained by further appropriately combining atactic polypropylene can be used. Alternatively, copolymers containing olefin monomers other than propylene can also be used. For example, propylene-α-olefin copolymers, which have a polypropylene crystalline portion and contain 15 mol% or more of α-olefins with 2 to 20 carbon atoms other than propylene, preferably one or more of the comonomers of ethylene, butene-1, 4-methylpentene-1, hexene-1, or octene-1, can be used. In addition, modifiers such as low-density polyethylene, ethylene-α-olefin copolymers, ethylene-propylene copolymer rubbers, ethylene-propylene-nonconjugated diene copolymer rubbers, styrene-butadiene copolymers, or hydrides, which are commonly used to soften polypropylene resins, can be appropriately added.

[0120] Additionally, as needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers may be added to the colored substrate layer 2.

[0121] The thickness of the colored substrate layer 2 is preferably in the range of 40 μm to 150 μm, more preferably 50 μm to 130 μm. This is because when the thickness of the colored substrate layer 2 is 40 μm or more, it can absorb unevenness and steps in the flooring material or the like used as the base, thereby allowing for a smoother installation of the decorative sheet 1. Furthermore, when the thickness of the colored substrate layer 2 is 150 μm or less, a colored substrate layer 2 exceeding the required thickness will not be formed, thus reducing the manufacturing cost of the decorative sheet 1.

[0122] Additionally, the colored substrate layer 2, for example, has a coloring density of 0.92 g / cm³. 3 The above is 1.12 g / cm³ 3 Within the range below, preferably 0.98 g / cm³ 3 The above 1.10 [g / cm] 3 The density within the following range.

[0123] The density of the colored substrate layer 2 was determined by method A in JIS K7112-1980 after annealing as described in JIS K6760-1995.

[0124] If the density of the colored substrate layer 2 is 0.92 g / cm³ 3 The above are those with a density less than 0.92 g / cm³. 3 Compared to the previous case, this improves the rigidity of the colored substrate layer 2. Furthermore, if the density of the colored substrate layer 2 is 1.12 g / cm³, the rigidity can be increased. 3 Below that, it is similar to a density exceeding 1.12 g / cm³. 3 Compared to the previous case, this can improve the transparency and mechanical strength of the colored substrate layer 2.

[0125] <Pattern Layer>

[0126] Pattern layer 3 is stacked on one side of colored substrate layer 2 (in) Figure 1 On the top side (the middle side), there is a layer for attaching patterns to give the design. It should be noted that if the coloring of the base material layer 2 can be used instead, the pattern layer 3 can also be omitted.

[0127] In addition, the pattern layer 3 is formed using printing inks or coatings. The printing inks or coatings that form the pattern layer 3 are formed, for example, by dissolving or dispersing colorants such as dyes or pigments together with a suitable binder resin in a suitable diluent.

[0128] The printing inks or coatings that form the pattern layer 3 are applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roller coating.

[0129] As an adhesive resin, for example, urethane resins, acrylic resins, vinyl chloroacetate resins, polyimide resins, nitrocellulose, or mixtures thereof can be used, but are not limited thereto.

[0130] As the pattern, any pattern can be used, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, text, symbols, single-color pigments, or combinations thereof. Furthermore, to improve the concealment of the decorative piece 1, a concealing layer can be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer can be formed, for example, using opaque printing inks or coatings containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0131] The thickness of the pattern layer 3 is preferably in the range of 1 μm to 10 μm. This is because when the thickness of the pattern layer 3 is 1 μm or more, the printing becomes clearer. In addition, when the thickness of the pattern layer 3 is 10 μm or less, the printability of the decorative sheet 1 is improved, and manufacturing costs can be reduced.

[0132] In addition, to impart various functions, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesives, desiccants, curing agents, curing accelerators, and curing delayers can be added to pattern layer 3.

[0133] Alternatively, the pattern layer 3 may be configured to have a solid-coated colored substrate layer to conceal the color / pattern of the base of the decorative piece 1, and a pattern layer for attaching a design-specific pattern.

[0134] <Adhesive Layer>

[0135] Adhesive layer 4 is stacked on one side of pattern layer 3 (in) Figure 1 On the top side (the middle side), there is a layer used to bond the pattern layer 3 and the transparent resin layer 5.

[0136] Materials used as adhesive layer 4 may include, for example, urethane-based, acrylic-based, olefin-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester-based, and polyolefin-based materials.

[0137] <Transparent resin layer>

[0138] The transparent resin layer 5 is stacked on one side of the adhesive layer 4 (in Figure 1 The top side is formed using a resin composition containing transparent plant-derived high-density polyethylene (e.g., "Green Polyethylene (SHC7260)" manufactured by Braskem).

[0139] It should be noted that the transparent resin layer 5 may also contain low-density polyethylene derived from plants, or linear low-density polyethylene derived from plants.

[0140] The density of the transparent resin layer 5 is, for example, 0.92 g / cm³. 3 Above 0.99 g / cm³ 3 Within the range below, preferably 0.94 g / cm³ 3 Above 0.98 g / cm³ 3 Within the range below, more preferably 0.95 g / cm³ 3 Above 0.97 g / cm³ 3 The density within the following range.

[0141] If the density of the transparent resin layer 5 is 0.92 g / cm³ 3 The above are those with a density less than 0.92 g / cm³. 3 Compared to the previous case, this improves the rigidity of the transparent resin layer 5. Furthermore, if the density of the transparent resin layer 5 is 0.99 g / cm³, the rigidity can be increased. 3Below that, it is related to a density exceeding 0.99 g / cm³. 3 Compared to the previous case, this can improve the transparency and mechanical strength of the transparent resin layer 5.

[0142] Alternatively, the transparent resin layer 5 can also be, for example, a resin with a density of 0.90 g / cm³. 3 Above 0.91 g / cm³ 3 The following range of plant-derived polypropylene.

[0143] A nucleating agent (e.g., "Rikemaster CN-002" manufactured by Ricken Vitamin Co., Ltd.) is added to the high-density polyethylene forming the transparent resin layer 5.

[0144] Based on the mass of high-density polyethylene, nucleating agents are added to high-density polyethylene in a range of 500 ppm to 2000 ppm.

[0145] In the first embodiment, as an example, the case in which a nucleating agent is added to high-density polyethylene in the range of 1,500 to 2,000 ppm is described based on the mass of high-density polyethylene.

[0146] As needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers can be added to the transparent resin layer 5.

[0147] It should be noted that the transparent resin layer 5 preferably has a degree of transparency (colorless transparent, colored transparent, semi-transparent) that allows the pattern of the pattern layer 3 to be seen through the surface (top) of the decorative sheet 1.

[0148] The thickness of the transparent resin layer 5 is, for example, set in the range of 20 μm to 200 μm, preferably in the range of 55 μm to 150 μm, and more preferably in the range of 60 μm to 80 μm.

[0149] <Surface Protective Layer>

[0150] Surface protective layer 6 is stacked on one side of transparent resin layer 5 (in) Figure 1 The middle (upper side) is a layer designed to give decorative piece 1 functions such as weather resistance, damage resistance, stain resistance, and design.

[0151] In addition, the surface protective layer 6 is formed, for example, using an acrylic resin composition.

[0152] In addition, depending on the requirements, the surface protective layer 6 may contain various additives such as weather resistant agents, plasticizers, stabilizers, fillers, dispersants, dyes, pigments and other colorants, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst trapping agents, colorants, light scattering agents, and gloss modifiers. Furthermore, depending on the requirements, the surface protective layer 6 may also contain functional additives such as antiviral agents, antibacterial agents, and antifungal agents.

[0153] <Concave and convex parts>

[0154] The uneven portion 7 is formed by recesses provided at multiple locations in the transparent resin layer 5 and the surface protective layer 6.

[0155] <Primer layer>

[0156] The primer layer 8 is a base layer used to improve the adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9.

[0157] In addition, the primer layer 8 is laminated on the other side of the colored substrate layer 2 (in Figure 1 (The middle is the lower side surface).

[0158] In addition, the primer layer 8 is formed, for example, using polyester resin, organic additives, pigments, etc.

[0159] In the second embodiment, as an example, the case in which the primer layer 8 is formed by crosslinking polyester polyol with isocyanate will be described.

[0160] It should be noted that, in order to improve corrosion resistance, anti-rust pigments can be added to the primer layer 8.

[0161] The thickness of the primer layer 8 is, for example, in the range of 1 [μm] to 10 [μm].

[0162] It should be noted that the above-described second embodiment is an example of the present invention. The present invention is not limited to the above-described second embodiment. Even in other embodiments, as long as they do not depart from the technical concept of the present invention, various changes can be made according to the design, etc.

[0163] (Effects of the second implementation method)

[0164] If it is the decorative piece 1 of the second embodiment, it can achieve the effects described below.

[0165] (1) It has a colored substrate layer 2 and a transparent resin layer 5 laminated on one side of the colored substrate layer 2. The transparent resin layer 5 is formed using a resin composition containing high-density polyethylene derived from plants, and a nucleating agent is added to the high-density polyethylene.

[0166] Therefore, even when using plant-derived materials, such as high-density polyethylene derived from plants, it is possible to form a transparent resin layer 5 with the same high hardness as that formed using polyethylene derived from fossil fuels.

[0167] As a result, even when using plant-derived materials, i.e., high-density polyethylene formed from plants, decorative sheets 1 can be provided that can suppress the reduction of surface hardness.

[0168] Furthermore, even when using plant-derived materials, such as high-density polyethylene derived from plants, it is possible to form a transparent resin layer 5 with the same high transparency as that formed using polyethylene derived from fossil fuels.

[0169] (2) Nucleating agent is added within the range of 500 ppm to 2000 ppm based on the mass of high-density polyethylene.

[0170] As a result, decorative sheets with less haze can be provided.

[0171] (3) Based on the mass of high-density polyethylene, add nucleating agent in the range of 1500 [ppm] to 2000 [ppm].

[0172] As a result, a decorative sheet with less haze can be provided compared to a composition with less than 1500 [ppm] nucleating agent added based on the mass of high-density polyethylene.

[0173] Furthermore, if the decorative material 10 of the second embodiment is used, the following effects can be achieved.

[0174] (4) Having a substrate 9 and a decorative sheet 1 laminated on at least one side of the substrate 9.

[0175] As a result, even when using plant-derived materials, i.e., high-density polyethylene formed from plants, decorative materials 10 can be provided that can suppress the reduction of surface hardness.

[0176] (Third implementation)

[0177] The following is for reference Figure 1 The composition of decorative material 10 is explained.

[0178] like Figure 1 As shown, the decorative material 10 includes a decorative piece 1 and a substrate 9.

[0179] It should be noted that the composition of the decorative material 10 in the third embodiment is the same as that in the first embodiment, except for the composition of the decorative piece 1. Therefore, the description of the composition other than the decorative piece 1 is omitted.

[0180] (Composition of decorative pieces)

[0181] like Figure 1 As shown, the decorative piece 1 has a colored substrate layer 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer 5, a surface protective layer 6, a raised and recessed portion 7, and a primer layer 8.

[0182] It should be noted that the decorative piece 1 in the third embodiment is the same as that in the first embodiment except for the composition of the colored substrate layer 2. Therefore, the description of the composition other than the colored substrate layer 2 is omitted.

[0183] <Colored substrate layer>

[0184] The structure of the colored substrate layer 2 is the same as that of the first embodiment described above, except that it is formed using a resin composition made by mixing high-density polyethylene and low-density polyethylene derived from plants.

[0185] High-density polyethylene derived from plants, such as "Green Polyethylene (SHC7260)" manufactured by Braskem.

[0186] Low-density polyethylene is, for example, polyethylene with a density of 0.94 or less.

[0187] In the third embodiment, as an example, the case in which the low-density polyethylene forming the colored substrate layer 2 is low-density polyethylene derived from plants will be described.

[0188] As a plant-derived low-density polyethylene, for example, "Green Polyethylene (SPB681)" manufactured by Braskem is used.

[0189] In addition, the low-density polyethylene forming the colored substrate layer 2 is included in the colored substrate layer 2 in a range of 5% to 30% by mass out of 100% by mass.

[0190] In the third embodiment, as an example, the case where the mixing ratio of high-density polyethylene and low-density polyethylene in the colored substrate layer 2 is in the range of 95:5 to 70:30 will be described.

[0191] It should be noted that the above-described third embodiment is an example of the present invention. The present invention is not limited to the above-described third embodiment. Even in other embodiments, as long as they do not depart from the technical concept of the present invention, various changes can be made according to the design, etc.

[0192] (Effects of the third embodiment)

[0193] If it is the decorative piece 1 of the third embodiment, it can achieve the effects described below.

[0194] (1) A colored substrate layer 2 is formed by using a resin composition made by mixing high-density polyethylene and low-density polyethylene derived from plants.

[0195] As a result, a decorative piece 1 can be provided that can suppress the reduction in bending machinability and machinability.

[0196] (2) The low-density polyethylene forming the colored substrate layer 2 is low-density polyethylene derived from plants.

[0197] As a result, the environmental impact can be reduced.

[0198] (3) The low-density polyethylene forming the colored substrate layer 2 is included in the colored substrate layer 2 in the range of 5% to 30% by mass of 100% by mass.

[0199] As a result, it is possible to suppress the reduction in film stability and strength of decorative sheet 1.

[0200] That is, when the content of low-density polyethylene is low, the film-forming stability of decorative sheet 1 is poor; when the content of low-density polyethylene is high, decorative sheet 1 becomes too soft. However, this problem can be solved by including the low-density polyethylene forming the colored substrate layer 2 in the colored substrate layer 2 in a range of 5% to 30% by mass out of 100% by mass.

[0201] (4) The mixing ratio of high-density polyethylene and low-density polyethylene in the colored substrate layer 2 is in the range of 95:5 to 70:30.

[0202] As a result, it is possible to suppress the reduction in film stability and strength of decorative sheet 1.

[0203] That is, when the content of low-density polyethylene is low, the film-forming stability of decorative sheet 1 is poor; when the content of low-density polyethylene is high, decorative sheet 1 becomes too soft. However, this problem can be solved by keeping the mixing ratio of high-density polyethylene to low-density polyethylene in the colored substrate layer 2 within the range of 95:5 to 70:30.

[0204] (Fourth implementation)

[0205] The following is for reference Figure 1 The composition of decorative material 10 is explained.

[0206] like Figure 1 As shown, the decorative material 10 includes a decorative piece 1 and a substrate 9.

[0207] It should be noted that the composition of the decorative material 10 in the fourth embodiment is the same as that in the first embodiment, except for the composition of the decorative piece 1. Therefore, the description of the composition other than the decorative piece 1 is omitted.

[0208] (Composition of decorative pieces)

[0209] like Figure 1 As shown, the decorative piece 1 has a colored substrate layer 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer 5, a surface protective layer 6, a raised and recessed portion 7, and a primer layer 8.

[0210] It should be noted that the decorative piece 1 in the fourth embodiment is the same as that in the second embodiment described above, except for the structure of the transparent resin layer 5. Therefore, the description of the structure other than the transparent resin layer 5 is omitted.

[0211] <Transparent resin layer>

[0212] The transparent resin layer 5 is formed using a resin composition made by mixing high-density polyethylene from plants and low-density polyethylene from plants, except that it is the same as the first embodiment described above.

[0213] In the fourth embodiment, as an example, the case where the mixing ratio of high-density polyethylene and low-density polyethylene in the transparent resin layer 5 is in the range of 80:20 to 60:40 will be described.

[0214] It should be noted that the above-described fourth embodiment is an example of the present invention. The present invention is not limited to the above-described fourth embodiment. Even in other embodiments, as long as they do not depart from the technical concept of the present invention, various changes can be made according to the design, etc.

[0215] (Effects of the fourth embodiment)

[0216] If it is the decorative piece 1 of the fourth embodiment, it can achieve the effects described below.

[0217] (1) The transparent resin layer 5 is formed using a resin composition made by mixing high-density polyethylene from plants and low-density polyethylene from plants.

[0218] As a result, the softness and transparency of the transparent resin layer 5 can be improved.

[0219] (2) The mixing ratio of high-density polyethylene and low-density polyethylene in the transparent resin layer 5 is in the range of 80:20 to 60:40.

[0220] As a result, the softness and transparency of the transparent resin layer 5 can be improved.

[0221] Example 2

[0222] Hereinafter, the decorative materials of Examples 1 to 22 and the decorative materials of Comparative Examples 1 to 5 will be described with reference to the second to fourth embodiments.

[0223] (Example 1)

[0224] The colored substrate layer is formed using colored polyethylene resin with a thickness of 55 μm.

[0225] The pattern layer is formed using urethane-based printing inks after corona discharge treatment is applied to one side of the colored substrate layer.

[0226] The adhesive layer is formed using a urethane-based adhesive.

[0227] The transparent resin layer is formed by adding "GreenPolyethylene" manufactured by Braskem, a plant-derived high-density polyethylene (HDPE), as a nucleating agent, "Rikemaster CN-002" manufactured by Riken Vitamin Co., Ltd., at a concentration of 1500 ppm relative to "Green Polyethylene" based on the mass of "Green Polyethylene". The thickness of the transparent resin layer is set to 70 μm.

[0228] The surface protective layer is formed with an acrylic resin composition as the main component.

[0229] The primer layer is made of polyester urethane resin. After corona discharge treatment is performed on one side of the colored substrate layer, the thickness is set to be between 1 μm and 2 μm.

[0230] Furthermore, by lamination, a decorative sheet of Example 1 with a thickness of 135 [μm] was formed.

[0231] After forming the decorative sheet of Example 1, the side of the primer layer opposite to the substrate is adhered to the substrate using "BA-10L (curing agent: BA-11B)" manufactured by Japan Coating Resin Corporation, thereby forming the decorative material of Example 1.

[0232] (Example 2)

[0233] Except for the addition of “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd. as a nucleating agent, which is 500 ppm based on the mass of high-density polyethylene, the decorative sheet and decorative material of Example 2 are formed in the same manner as in Example 1.

[0234] (Example 3)

[0235] Except for the addition of “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd. as a nucleating agent, which is 2000 [ppm] based on the mass of high-density polyethylene, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Example 3.

[0236] (Example 4)

[0237] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 95:5 is used to form the colored substrate layer, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Example 4.

[0238] (Example 5)

[0239] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 95:5 is used to form the colored substrate layer, it is formed in the same manner as in Example 2, thereby forming the decorative sheet and decorative material of Example 5.

[0240] (Example 6)

[0241] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 95:5 is used to form the colored substrate layer, it is formed in the same manner as in Example 3, thereby forming the decorative sheet and decorative material of Example 6.

[0242] (Example 7)

[0243] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 70:30 is used to form the colored substrate layer, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Example 7.

[0244] (Example 8)

[0245] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 70:30 is used to form the colored substrate layer, it is formed in the same manner as in Example 2, thereby forming the decorative sheet and decorative material of Example 8.

[0246] (Example 9)

[0247] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 70:30 is used to form the colored substrate layer, it is formed in the same manner as in Example 3, thereby forming the decorative sheet and decorative material of Example 9.

[0248] (Example 10)

[0249] Except that a transparent resin layer is formed by mixing a resin composition of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) derived from plants in a ratio of 80:20, the same process as in Example 4 is used to form the decorative sheet and decorative material of Example 10.

[0250] (Example 11)

[0251] Except that a transparent resin layer is formed by mixing a resin composition of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) derived from plants in a ratio of 80:20, the same process as in Example 5 is used to form the decorative sheet and decorative material of Example 11.

[0252] (Example 12)

[0253] Except that a transparent resin layer is formed by mixing a resin composition of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) derived from plants in a ratio of 80:20, the same process as in Example 6 is used to form the decorative sheet and decorative material of Example 12.

[0254] (Example 13)

[0255] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 70:30 is used to form the colored substrate layer, it is formed in the same manner as in Example 10, thereby forming the decorative sheet and decorative material of Example 13.

[0256] (Example 14)

[0257] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 70:30 is used to form the colored substrate layer, it is formed in the same manner as in Example 11, thereby forming the decorative sheet and decorative material of Example 14.

[0258] (Example 15)

[0259] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 70:30 is used to form the colored substrate layer, it is formed in the same manner as in Example 12, thereby forming the decorative sheet and decorative material of Example 15.

[0260] (Example 16)

[0261] Except that a transparent resin layer is formed using a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 60:40, the same method as in Example 10 is used to form the decorative sheet and decorative material of Example 16.

[0262] (Example 17)

[0263] Except that a transparent resin layer is formed by mixing a resin composition of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 60:40, the same process as in Example 11 is used to form the decorative sheet and decorative material of Example 17.

[0264] (Example 18)

[0265] Except that a transparent resin layer is formed by mixing a resin composition of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) derived from plants in a ratio of 60:40, it is formed in the same manner as in Example 12, thereby forming the decorative sheet and decorative material of Example 18.

[0266] (Example 19)

[0267] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 70:30 is used to form the colored substrate layer, it is formed in the same manner as in Example 16, thereby forming the decorative sheet and decorative material of Example 19.

[0268] (Example 20)

[0269] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 70:30 is used to form the colored substrate layer, it is formed in the same manner as in Example 17, thereby forming the decorative sheet and decorative material of Example 20.

[0270] (Example 21)

[0271] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 70:30 is used to form the colored substrate layer, it is formed in the same manner as in Example 18, thereby forming the decorative sheet and decorative material of Example 21.

[0272] (Example 22)

[0273] Except for the use of maleic anhydride-modified polyethylene resin to form the adhesive layer, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Example 22.

[0274] (Comparative Example 1)

[0275] Except that no nucleating agent is added to the high-density polyethylene, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Comparative Example 1.

[0276] (Comparative Example 2)

[0277] Except that a transparent resin layer is formed using polyethylene made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a 50:50 ratio, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Comparative Example 2.

[0278] (Comparative Example 3)

[0279] Except that no nucleating agent is added to the high-density polyethylene, it is formed in the same way as Comparative Example 2, thereby forming the decorative sheet and decorative material of Comparative Example 3.

[0280] (Comparative Example 4)

[0281] Except for the fact that a transparent resin layer is formed from low-density polyethylene (LDPE) derived from plants, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Comparative Example 4.

[0282] (Comparative Example 5)

[0283] Except that a resin composition made by mixing high-density polyethylene (HDPE) and low-density polyethylene (LDPE) from plants in a ratio of 60:40 is used to form the colored substrate layer, it is formed in the same manner as in Example 1, thereby forming the decorative sheet and decorative material of Comparative Example 5.

[0284] (Performance evaluation, evaluation results)

[0285] For the decorative materials of Examples 1 to 22 and the decorative materials of Comparative Examples 1 to 5, surface hardness, productivity, transmittance, haze, bending processability, and machinability were evaluated. The methods described below were used as evaluation methods.

[0286] <Surface Hardness>

[0287] After conducting pencil hardness tests on decorative materials using pencils of varying hardness, the surface hardness was evaluated by identifying any damage (dents) on the surface (protective layer). Damage occurring after testing with a pencil with a hardness of 2B or higher was rated as "◎", while damage occurring after testing with a pencil with a hardness of 4B or higher was rated as "○". Furthermore, damage occurring after testing with a pencil with a hardness of 5B or lower was rated as "×".

[0288] Productivity

[0289] Productivity is evaluated based on whether any problems exist in the manufacturing of the decorative sheet. Then, a "◎" is awarded for cases where there are no problems in the manufacturing of the decorative sheet, a "○" is awarded for cases where there are no production problems in the manufacturing of the decorative sheet, and a "×" is awarded for cases where there are problems in the manufacturing of the decorative sheet.

[0290] <Transparency>

[0291] With the thickness of the transparent resin layer set between 70 μm and 80 μm, the total light transmittance at a wavelength of 555 nm was measured using a spectrophotometer (integrating sphere) to evaluate the transmittance. A total light transmittance of 85% was rated as "◎", a total light transmittance between 80% and 85% was rated as "○", and a total light transmittance less than 80% was rated as "×".

[0292] <Haze>

[0293] The haze of the transparent resin layer was measured using a UV-Vis-NIR spectrophotometer (Shimadzu Corporation: "UV-3600").

[0294] When measuring the haze percentage of the transparent resin layer, firstly, resin with the same composition as the transparent resin layer of the decorative sheets of Examples 1 to 22 and the transparent resin layer of the decorative sheets of Comparative Examples 1 to 5 was extruded to form a resin film with a thickness set in the range of 70 [μm] to 80 [μm]. Next, the haze at a wavelength of 555 [nm] was measured using a spectrophotometer (integrating sphere), and the haze was evaluated. Then, cases with a haze of less than 15% were evaluated as "◎", cases with a haze of 15% or more but less than 25% were evaluated as "○", and cases with a haze of 25% or more were evaluated as "×".

[0295] <Bending process suitability>

[0296] Using decorative sheets (i.e., decorative materials) pasted onto MDF (Medium Density Fiberboard), confirm the suitability for V-cutting (with or without bending whitening) and evaluate the suitability for bending. Then, cases without whitening are rated as "○" (pass), cases with slight whitening are rated as "△" (pass), and cases with whitening are rated as "×" (fail).

[0297] <Machinability>

[0298] The decorative pieces (i.e., decorative materials) pasted on the MDF were cut using a circular saw and then cut into the MDF using a handheld router. The condition of the burrs on the decorative pieces was checked, and the machinability was evaluated. Then, the case where no burrs were generated was evaluated as "○", and the case where burrs were generated almost completely and were difficult to correct was evaluated as "×".

[0299]

[0300]

[0301] The results of evaluating various properties using the above method show that the decorative materials of Examples 1 to 22 exhibited excellent performance in all evaluation tests. On the other hand, the decorative materials of Comparative Examples 1 to 5 did not exhibit excellent performance in all evaluation tests.

[0302] (Fifth implementation)

[0303] The following is for reference Figure 1 The composition of decorative material 10 is explained.

[0304] like Figure 1As shown, the decorative material 10 comprises a decorative piece 1 and a substrate 9. It should be noted that the specific composition of the decorative piece 1 will be described later.

[0305] It should be noted that the composition of the decorative material 10 in the fifth embodiment is the same as that in the first embodiment, except for the composition of the decorative piece 1. Therefore, the description of the composition other than the decorative piece 1 is omitted.

[0306] (Composition of decorative pieces)

[0307] like Figure 1 As shown, the decorative piece 1 has a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface protective layer 6, a raised and recessed portion 7, and a primer layer 8.

[0308] <Colored substrate layer>

[0309] The colored substrate layer 2 is a resin layer formed using thermoplastic resin, which is a colored resin layer formed from a resin composition containing polyethylene derived from biomass (from plants).

[0310] The composition of the colored substrate layer 2 will be described in detail below.

[0311] (Polyethylene derived from biomass)

[0312] In the fifth embodiment, the polyethylene derived from biomass is polymerized from monomers containing ethylene derived from biomass. There is no particular limitation on the ethylene derived from biomass; ethylene produced by conventionally known methods can be used. Since ethylene derived from biomass is used as the monomer source, the polymerized polyethylene is derived from biomass.

[0313] It should be noted that the raw material monomers of polyethylene may not contain 100% by mass ethylene derived from biomass.

[0314] The monomers used as raw materials for polyethylene derived from biomass may further contain at least one of ethylene derived from fossil fuels and α-olefins derived from fossil fuels, or may further contain α-olefins derived from biomass.

[0315] There is no particular limitation on the number of carbon atoms in the aforementioned α-olefins; α-olefins with 3 to 20 carbon atoms are generally used, with butene, hexene, or octene being preferred. This is because butene, hexene, or octene can be manufactured by polymerizing ethylene, which is a feedstock derived from biomass. Furthermore, by containing such α-olefins, the polymerized polyethylene has an alkyl group as a branched structure, thus making it more flexible than simple linear polyethylene.

[0316] By using ethylene as a feedstock from biomass, it is theoretically possible to produce it from 100% biomass components.

[0317] The ethylene concentration from biomass in the aforementioned polyethylene (hereinafter sometimes referred to as "biomass content") is a value obtained by measuring the carbon content from biomass using radiocarbon (C14) determination. It is known that atmospheric carbon dioxide contains a certain proportion (105.5 pMC) of C14; therefore, the C14 content in plants that absorb atmospheric carbon dioxide (e.g., corn) is also approximately 105.5 pMC. Furthermore, it is known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in polyethylene, the proportion of carbon from biomass can be calculated. In the fifth embodiment, the carbon content from biomass, Pbio, when the C14 content in polyethylene is set to PC14, can be calculated as follows.

[0318] Pbio (%) = PC14 / 105.5 × 100

[0319] In the fifth embodiment, theoretically, if all ethylene from biomass is used as the raw material for polyethylene, the concentration of ethylene from biomass is 100%, and the biomass degree of the polyethylene from biomass is 100. Furthermore, in fossil fuel polyethylene manufactured solely from fossil fuel raw materials, the concentration of ethylene from biomass is 0%, and the biomass degree of the polyethylene from fossil fuels is 0.

[0320] In the fifth embodiment, the polyethylene derived from biomass or the decorative sheet containing such polyethylene does not require a biomass content of 100.

[0321] In the fifth embodiment, the polymerization method for monomers containing ethylene derived from biomass is not particularly limited, and can be carried out using conventionally known methods. The polymerization temperature and polymerization pressure can be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and conventionally known apparatus can be used. Hereinafter, an example of a polymerization method for monomers containing ethylene will be described.

[0322] The polymerization method for ethylene polymers or copolymers of ethylene and α-olefins can be appropriately selected based on the type of target polyethylene, such as the density or branching of high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). For example, it is preferable to use multi-site catalysts such as Ziegler-Natta catalysts or single-site catalysts such as metallocene catalysts as polymerization catalysts, and to carry out the polymerization in one or more stages using any of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[0323] In addition, polyethylene derived from biomass can be a polymer of ethylene alone or a copolymer of ethylene and α-olefins, or a mixture of two or more.

[0324] (A resin composition containing polyethylene derived from biomass)

[0325] In the fifth embodiment, the resin composition contains the aforementioned polyethylene as a main component. The resin composition contains at least 5% by mass, preferably 5 to 95% by mass, and more preferably 25 to 75% by mass of ethylene derived from biomass relative to the total resin composition. If the concentration of ethylene derived from biomass in the resin composition is 5% by mass or more, the amount of fossil fuel used can be reduced compared to conventional methods, enabling the achievement of carbon-neutral decorative sheets.

[0326] The above-mentioned resin composition may contain two or more types of polyethylene with different biomass concentrations, as long as the concentration of ethylene from biomass as a whole is within the above-mentioned range.

[0327] The resin composition described above may further contain polyethylene derived from fossil fuels, which is obtained by polymerizing a monomer containing at least one of ethylene and α-olefins derived from fossil fuels, and ethylene derived from fossil fuels. That is, in the fifth embodiment, the resin composition may also be a mixture of polyethylene derived from biomass and polyethylene derived from fossil fuels. There is no particular limitation on the mixing method; conventionally known methods can be used. For example, dry blending or melt blending may be used.

[0328] According to the fifth embodiment, the resin composition contains preferably 5 to 90% by mass, more preferably 25 to 75% by mass, of polyethylene derived from biomass; and preferably 10 to 95% by mass, more preferably 25 to 75% by mass, of polyethylene derived from fossil fuels. Even when using a resin composition with such a mixture, as long as the concentration of ethylene derived from biomass as a whole is within the above-mentioned range, it is acceptable.

[0329] In the resin composition manufactured in the above-described resin composition manufacturing process, various additives may be added in addition to polyethylene as the main component, without impairing its properties. Examples of additives include plasticizers, UV stabilizers, anti-staining agents, matting agents, deodorizers, flame retardants, weathering agents, antistatic agents, yarn friction reducers, slip agents, anti-sticking agents, antioxidants, ion exchangers, and coloring pigments. These additives are preferably added in the range of 1 to 20% by mass, more preferably 1 to 10% by mass, relative to the total resin composition.

[0330] As described above, the coloring substrate layer 2 contains ethylene derived from biomass at a concentration of 5% or more by mass relative to the total amount of the coloring substrate layer 2, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass. If the concentration of ethylene derived from biomass in the coloring substrate layer 2 is 5% or more by mass, the amount of fossil fuel used can be reduced compared to the past, and a carbon-neutral decorative sheet can be achieved.

[0331] The colored substrate layer 2 has a density of 0.92 g / cm³. 3 The above is 1.12 g / cm³ 3 Within the range below, preferably 0.98 g / cm³ 3 The above 1.10 [g / cm] 3 The density is within the range below. The density of the colored substrate layer 2 is determined by method A specified in JIS K7112-1980 after annealing as described in JIS K6760-1995. If the density of the colored substrate layer 2 is 0.92 g / cm³, the density is determined by the following method. 3 The above can improve the rigidity of the colored substrate layer 2. Additionally, if the density of the colored substrate layer 2 is 1.12 g / cm³, the rigidity of the substrate layer 2 can be improved. 3 The following steps can improve the transparency and mechanical strength of the colored substrate layer 2.

[0332] In the colored substrate layer 2, the polyethylene derived from biomass can be any of the following: polyethylene comprising high-density polyethylene and low-density polyethylene derived from biomass; polyethylene comprising high-density polyethylene derived from biomass and low-density polyethylene derived from fossil fuels; or polyethylene comprising low-density polyethylene derived from biomass within high-density polyethylene derived from fossil fuels.

[0333] The overall biomass content of the colored substrate layer 2 can be in the range of 10% to 90%.

[0334] It should be noted that high-density polyethylene derived from biomass refers to polyethylene with a density exceeding 0.94. Conversely, low-density polyethylene derived from biomass refers to polyethylene with a density below 0.94.

[0335] In the colored substrate layer 2, the polyethylene derived from biomass can be a blend of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) (which can be derived from either biomass or fossil fuels) in a ratio ranging from 95:5 to 70:30. When the content of LDPE is low, the film-forming stability is poor; when the content of LDPE is high, the film becomes too soft.

[0336] The manufacturing method of the colored substrate layer 2 is not particularly limited and can be manufactured by conventionally known methods. In the fifth embodiment, it is preferably formed by calendering.

[0337] Additionally, as needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers may be added to the colored substrate layer 2.

[0338] The thickness of the colored substrate layer 2 is preferably in the range of 40 μm to 200 μm, more preferably 51 μm to 120 μm, and even more preferably 55 μm to 100 μm. This is because when the thickness of the colored substrate layer 2, which is made of polyethylene derived from biomass, is 40 μm or more, it can absorb unevenness and steps in the flooring material or the like used as the substrate, thereby allowing for a good installation of the decorative sheet 1. Furthermore, when the thickness of the colored substrate layer 2 is 200 μm or less, a colored substrate layer 2 exceeding the required thickness will not be formed, thereby reducing the manufacturing cost of the decorative sheet 1.

[0339] It should be noted that in the fifth embodiment, polyethylene derived from biomass was described as the resin constituting the coloring substrate layer 2, but the present invention is not limited thereto. For example, polypropylene or polybutene derived from biomass may be used instead of the aforementioned polyethylene derived from biomass. That is, in the fifth embodiment, polyolefins derived from biomass can be widely used as the resin constituting the coloring substrate layer 2.

[0340] <Pattern Layer>

[0341] Pattern layer 3 is stacked on one side of colored substrate layer 2 (in) Figure 1 On the top side (the middle side), there is a layer for attaching patterns to give the design. It should be noted that if the coloring of the base material layer 2 can be used instead, the pattern layer 3 can also be omitted.

[0342] In addition, the pattern layer 3 is formed using printing inks or coatings. The printing inks or coatings that form the pattern layer 3 are formed, for example, by dissolving or dispersing colorants such as dyes or pigments together with a suitable binder resin in a suitable diluent.

[0343] The printing inks or coatings that form the pattern layer 3 are applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roller coating.

[0344] As an adhesive resin, for example, urethane resins, acrylic resins, vinyl chloroacetate resins, polyimide resins, nitrocellulose, or mixtures thereof can be used, but are not limited thereto.

[0345] As the pattern, any pattern can be used, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, text, symbols, single-color pigments, or combinations thereof. Furthermore, to improve the concealment of the decorative piece 1, a concealing layer can be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer can be formed, for example, using opaque printing inks or coatings containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0346] The thickness of the pattern layer 3 is preferably in the range of 1 μm to 10 μm. This is because when the thickness of the pattern layer 3 is 1 μm or more, the printing becomes clearer. In addition, when the thickness of the pattern layer 3 is 10 μm or less, the printability of the decorative sheet 1 is improved, and manufacturing costs can be reduced.

[0347] In addition, to impart various functions, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesives, desiccants, curing agents, curing accelerators, and curing delayers can be added to pattern layer 3.

[0348] Alternatively, the pattern layer 3 may be configured to have a solid-coated colored substrate layer to conceal the color / pattern of the base of the decorative piece 1, and a pattern layer for attaching a design-specific pattern.

[0349] <Adhesive Layer>

[0350] Adhesive layer 4 is stacked on one side of pattern layer 3 (in) Figure 1 On the top side (the middle side), there is a layer used to bond the pattern layer 3 and the transparent resin layer 5.

[0351] Materials used for adhesive layer 4 include, for example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, and polyolefin-based resins. In particular, considering adhesion to the transparent resin layer 5, polyolefin-based resins are preferred.

[0352] <Transparent resin layer>

[0353] The transparent resin layer 5 is stacked on one side of the adhesive layer 4 (in Figure 1On the upper side (the middle side), there is a transparent resin layer formed of a resin composition containing the aforementioned polyethylene derived from biomass (from plants). More specifically, the transparent resin layer 5 is a resin layer formed of a resin composition containing polyethylene derived from biomass, which is polymerized from monomers containing ethylene derived from the aforementioned biomass. That is, in the transparent resin layer 5, a resin composition containing polyethylene derived from biomass used in the colored substrate layer 2 may also be used. In addition, it may contain polyethylene derived from fossil fuels, which is polymerized from monomers containing at least one of ethylene and α-olefins derived from fossil fuels and ethylene derived from fossil fuels.

[0354] The transparent resin layer 5 may contain ethylene derived from biomass at a concentration of 5% or more by mass relative to the total amount of the transparent resin layer 5, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass. If the concentration of ethylene derived from biomass in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the past, and a carbon-neutral decorative sheet can be achieved.

[0355] The density of the transparent resin layer 5 is 0.92 g / cm³. 3 Above 0.99 g / cm³ 3 Within the range below, preferably 0.94 g / cm³ 3 Above 0.98 g / cm³ 3 Within the range below, more preferably 0.95 g / cm³ 3 Above 0.97 g / cm³ 3 The density is within the range below. The density of the transparent resin layer 5 is determined by method A specified in JIS K7112-1980 after annealing as described in JIS K6760-1995. If the density of the transparent resin layer 5 is 0.92 g / cm³... 3 The above can improve the rigidity of the transparent resin layer 5. Additionally, if the density of the transparent resin layer 5 is 0.99 g / cm³, the rigidity can be increased. 3 The following steps can improve the transparency and mechanical strength of the transparent resin layer 5.

[0356] The transparent resin layer 5 has a thickness of 55-150 μm, preferably 55-100 μm, and more preferably 60-80 μm.

[0357] The transparent resin layer 5 may contain high-density polyethylene derived from biomass as the biomass-derived polyethylene.

[0358] In addition, the transparent resin layer 5 may contain polyethylene derived from biomass, which is a blend of high-density polyethylene from biomass and low-density polyethylene from biomass in the range of 100:0 to 20:80.

[0359] In addition, the overall biomass content of the transparent resin layer 5 can be in the range of 10% to 90%.

[0360] The manufacturing method of the transparent resin layer 5 is not particularly limited and can be manufactured by conventionally known methods. In the fifth embodiment, it is preferably formed by extrusion molding, and more preferably by T-die molding or blow molding.

[0361] In the fifth embodiment, the transparent resin layer 5 and the colored substrate layer 2 preferably satisfy the following specific relationships regarding density, thickness, and biomass density (ethylene concentration from biomass).

[0362] In the fifth embodiment, the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 preferably satisfy d2>d1. This is because formability is required for the transparent resin layer 5 to function, and productivity is required for the colored substrate layer 2 to function.

[0363] It should be noted that the ratio (d2 / d1) of the density d1 of the transparent resin layer 5 to the density d2 of the colored substrate layer 2 is preferably in the range of 1.1 to 1.5, more preferably in the range of 1.1 to 1.3, and even more preferably in the range of 1.1 to 1.2. By ensuring that the density ratio of the transparent resin layer to the colored substrate layer is within this range, even when using polyethylene derived from biomass, it can possess the extrusion suitability and bending processing suitability required for decorative sheets.

[0364] In the fifth embodiment, the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored substrate layer 2 preferably satisfy t1 ≥ t2. This is because a thickness is required for the transparent resin layer 5 to function, but a thickness similar to that of the transparent resin layer 5 is not required for the colored substrate layer 2 to function.

[0365] It should be noted that the ratio (t1 / t2) of the thickness t1 of the transparent resin layer 5 to the thickness t2 of the colored substrate layer 2 is preferably in the range of 1.1 to 3, more preferably in the range of 1.1 to 2, and even more preferably in the range of 1.1 to 1.5.

[0366] In the fifth embodiment, the ethylene concentration C1 from biomass in the transparent resin layer 5 and the ethylene concentration C2 from biomass in the colored substrate layer 2 preferably satisfy C1 > C2. This is because, since the transparent resin layer 5 is thick and uses a large amount of ethylene in order to function as a transparent resin layer 5, the amount of fossil fuel used can be further reduced by increasing the biomass content of the transparent resin layer 5.

[0367] Nucleating agents (e.g., "Rikemaster CN-002" manufactured by RichenVitamin Co., Ltd.) may also be added to the biomass-derived polyethylene that forms the transparent resin layer 5.

[0368] Based on the mass of polyethylene, the nucleating agent is preferably added to polyethylene in the range of 500 to 2000 ppm, and more preferably in the range of 1500 to 2000 ppm.

[0369] As needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers can be added to the transparent resin layer 5.

[0370] It should be noted that the transparent resin layer 5 preferably has a degree of transparency (colorless transparent, colored transparent, semi-transparent) that allows the pattern of the pattern layer 3 to be seen through the surface (top) of the decorative sheet 1.

[0371] It should be noted that in the fifth embodiment, polyethylene derived from biomass was described as the biomass-derived resin constituting the transparent resin layer 5, but the present invention is not limited thereto. For example, polypropylene or polybutene derived from biomass may be used instead of the aforementioned biomass-derived polyethylene. That is, in the fifth embodiment, polyolefins derived from biomass can be widely used as the biomass-derived resin constituting the transparent resin layer 5.

[0372] <Surface Protective Layer>

[0373] Surface protective layer 6 is stacked on one side of transparent resin layer 5 (in) Figure 1 The middle (upper side) is a layer designed to give decorative piece 1 functions such as weather resistance, damage resistance, stain resistance, and design.

[0374] Alternatively, the surface protective layer 6 can be formed using a thermosetting resin, an ionizing radiation-cured resin, or, for example, an acrylic resin composition.

[0375] In addition, depending on the requirements, the surface protective layer 6 may contain various additives such as weather resistant agents, plasticizers, stabilizers, fillers, dispersants, dyes, pigments and other colorants, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst trapping agents, colorants, light scattering agents, and gloss modifiers. Furthermore, depending on the requirements, the surface protective layer 6 may also contain functional additives such as antibacterial agents and antifungal agents.

[0376] <Concave and convex parts>

[0377] The uneven portion 7 is formed by recesses provided at multiple locations in the transparent resin layer 5 and the surface protective layer 6.

[0378] <Primer layer>

[0379] The primer layer 8 is a base layer used to improve the adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9.

[0380] In addition, the primer layer 8 is laminated on the other side of the colored substrate layer 2 (in Figure 1 (The middle is the lower side surface).

[0381] In addition, the primer layer 8 is formed, for example, using polyester resin, organic additives, pigments, etc.

[0382] It should be noted that, in order to improve corrosion resistance, anti-rust pigments can be added to the primer layer 8.

[0383] The thickness of the primer layer 8 is, for example, in the range of 1 [μm] to 10 [μm].

[0384] It should be noted that the above-described embodiments are an example of the present invention. The present invention is not limited to the above-described embodiments. Even in ways other than those described, as long as they do not depart from the technical concept of the present invention, various changes can be made according to the design, etc.

[0385] (Effects of the fifth embodiment)

[0386] If it is the decorative piece 1 of the fifth embodiment, it can achieve the effects described below.

[0387] (1) The colored substrate layer 2 and the transparent resin layer 5 are resin layers formed from a resin composition containing polyethylene derived from biomass, which is polymerized from monomers containing ethylene derived from biomass. The transparent resin layer 5 contains ethylene derived from biomass and has a content of 0.92 g / cm³. 3 Above 0.99 g / cm³ 3 The density is within the range of 55 μm to 150 μm, and the colored substrate layer 2 contains ethylene from biomass with a density of 0.92 g / cm³. 3 The above is 1.12 g / cm³ 3 Density within the range of 51 μm to 120 μm and thickness within the range of 120 μm.

[0388] Therefore, even when using materials derived from plants, such as polyethylene derived from biomass, it is possible to form a colored substrate layer 2 and a transparent resin layer 5 with the same high hardness as those formed using materials such as polypropylene.

[0389] As a result, even when using plant-derived materials, i.e., polyethylene formed from biomass, decorative sheets 1 can be provided that can suppress the reduction of surface hardness.

[0390] Furthermore, even when using materials derived from plants, such as polyethylene derived from biomass, a transparent resin layer 5 with the same high transparency as that formed using materials such as polypropylene can be formed.

[0391] (2) At least one of the transparent resin layer 5 and the colored substrate layer 2 contains high-density polyethylene from biomass and low-density polyethylene from biomass as the polyethylene from biomass.

[0392] As a result, a transparent resin layer 5 and a colored substrate layer 2 with further flexibility can be formed.

[0393] (3) The transparent resin layer 5 contains polyethylene derived from biomass, which is a blend of high-density polyethylene derived from biomass and low-density polyethylene derived from biomass in a ratio of 100:0 to 20:80. As a result, a transparent resin layer 5 with higher hardness can be formed.

[0394] (4) The colored substrate layer 2 contains high-density polyethylene and low-density polyethylene derived from biomass as the polyethylene derived from biomass, and the biomass content is in the range of 10% to 90%.

[0395] As a result, a colored substrate layer 2 with good film-forming stability and sufficient flexibility as a decorative sheet can be formed.

[0396] (5) When the density of the transparent resin layer 5 is set to d1 and the density of the colored substrate layer 2 is set to d2, d2>d1 is satisfied.

[0397] As a result, decorative sheets 1 with sufficient extrusion adaptability can be formed.

[0398] (6) When the thickness of the transparent resin layer 5 is set to t1 and the thickness of the colored substrate layer 2 is set to t2, t1≥t2 is satisfied.

[0399] As a result, a decorative piece 1 with sufficient flexibility in bending processing can be formed.

[0400] Furthermore, if the decorative material 10 of the fifth embodiment is used, the following effects can be achieved.

[0401] (7) A decorative sheet 1 having a substrate 9 and a decorative sheet 1 laminated on at least one side of the substrate 9.

[0402] As a result, even when using plant-derived materials, i.e., polyethylene formed from biomass, decorative materials 10 can be provided that can suppress the reduction of surface hardness.

[0403] 3rd Embodiment

[0404] Hereinafter, the decorative materials of Examples 1 to 11 and the decorative materials of Comparative Examples 1 to 5 will be described with reference to the fifth embodiment.

[0405] (Example 1)

[0406] After applying corona discharge treatment to one side of the substrate, a pattern layer printed with urethane-based printing ink, a urethane-based adhesive layer, a maleic anhydride-modified polyethylene resin layer (transparent adhesive layer), a transparent resin layer, and a surface protective layer mainly composed of an acrylic resin composition are sequentially layered on that side of the substrate. Furthermore, after applying corona discharge treatment to the other side of the substrate, a primer layer (thickness: 1–2 μm) composed of polyester urethane resin is formed. Thus, the decorative sheet of Example 1 (total thickness: 135 μm) is obtained.

[0407] In Example 1, a colored substrate layer (thickness: 55 μm) was used as the substrate, formed from a resin composition containing high-density polyethylene from biomass and low-density polyethylene from fossil fuels. The colored substrate layer was obtained by calendering this resin composition. The biomass content of the thus formed colored substrate layer was 80%, and the density of the colored substrate layer was 1.08 g / cm³. 3 ].

[0408] For the transparent resin layer, a transparent resin layer (thickness: 80 μm) is formed using a resin composition containing biomass-derived polyethylene (Braskem Corporation's "Biomass Polyethylene"). This biomass-derived polyethylene is a resin obtained by blending high-density polyethylene (SHC7260) and low-density polyethylene (SPB681) derived from biomass at a ratio (high-density polyethylene / low-density polyethylene) of 80 / 20. The transparent resin layer is obtained by extrusion lamination of this resin. The resulting transparent resin layer has a biomass content of 94% and a density of 0.95 g / cm³. 3 ].

[0409] (Example 2)

[0410] Using "biomass polyethylene" manufactured by Braskem, high-density polyethylene (SHC7260) and low-density polyethylene (SPB681) derived from biomass were blended at a ratio of 100 / 0 (high-density polyethylene / low-density polyethylene). A transparent resin layer was obtained by extrusion lamination of this resin. Otherwise, the decorative sheet of Example 2 was obtained in the same manner as in Example 1. It should be noted that the biomass content of the resulting transparent resin layer was 94%, and the density was 0.96 g / cm³. 3 ].

[0411] (Example 3)

[0412] Using "biomass polyethylene" manufactured by Braskem, high-density polyethylene (SHC7260) and low-density polyethylene (SPB681) derived from biomass were blended in a ratio of 60 / 40 (high-density polyethylene / low-density polyethylene). A transparent resin layer was obtained by extrusion lamination of this resin. Otherwise, the decorative sheet of Example 3 was obtained in the same manner as in Example 1. It should be noted that the density of the transparent resin layer thus formed is 0.94 g / cm³. 3 ].

[0413] (Example 4)

[0414] Using "biomass polyethylene" manufactured by Braskem, high-density polyethylene (SHC7260) and low-density polyethylene (SPB681) derived from biomass were blended in a 50 / 50 ratio (high-density polyethylene / low-density polyethylene). A transparent resin layer was obtained by extrusion lamination of this resin. Otherwise, the decorative sheet of Example 4 was obtained in the same manner as in Example 1. It should be noted that the density of the transparent resin layer thus formed is 0.93 g / cm³. 3 ].

[0415] (Example 5)

[0416] Using "biomass polyethylene" manufactured by Braskem, high-density polyethylene (SHC7260) and low-density polyethylene (SPB681) derived from biomass were blended in a ratio of 30 / 70 (high-density polyethylene / low-density polyethylene). A transparent resin layer was obtained by extrusion lamination of this resin. Otherwise, the decorative sheet of Example 5 was obtained in the same manner as in Example 1. It should be noted that the density of the transparent resin layer thus formed is 0.92 g / cm³. 3 ].

[0417] (Example 6)

[0418] Except that the thickness of the transparent resin layer was set to 55 μm and the thickness of the colored substrate layer was set to 55 μm, the decorative sheet of Example 6 was obtained in the same manner as in Example 1.

[0419] (Example 7)

[0420] Except that the thickness of the transparent resin layer was set to 150 μm, the decorative sheet of Example 7 was obtained in the same manner as in Example 1.

[0421] (Example 8)

[0422] In addition to setting the density of the colored substrate layer to 0.92 g / cm³, 3 In addition, the decorative sheet of Example 8 was obtained in the same manner as in Example 1.

[0423] (Example 9)

[0424] In addition to setting the density of the colored substrate layer to 1.12 g / cm³, 3 In addition, the decorative sheet of Example 9 was obtained in the same manner as in Example 1.

[0425] (Example 10)

[0426] Except that the thickness of the colored substrate layer was set to 51 μm, the decorative sheet of Example 10 was obtained in the same manner as in Example 1.

[0427] (Example 11)

[0428] Except that the thickness of the colored substrate layer was set to 120 μm, the decorative sheet of Example 11 was obtained in the same manner as in Example 1.

[0429] (Comparative Example 1)

[0430] Using "biomass polyethylene" manufactured by Braskem, high-density polyethylene (SHC7260) and low-density polyethylene (SPB681) derived from biomass were blended at a ratio of 0 / 100 (high-density polyethylene / low-density polyethylene). A transparent resin layer was obtained by extrusion lamination of this resin. Otherwise, the decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1. It should be noted that the density of the transparent resin layer thus formed is 0.91 g / cm³. 3 ].

[0431] (Comparative Example 2)

[0432] Except that the thickness of the transparent resin layer was set to 30 μm, the decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1.

[0433] (Comparative Example 3)

[0434] Except that the thickness of the transparent resin layer was set to 200 μm, the decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1.

[0435] (Comparative Example 4)

[0436] Except that the thickness of the colored substrate layer was set to 40 μm, the decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1.

[0437] (Comparative Example 5)

[0438] Except that the thickness of the colored substrate layer was set to 150 μm, the decorative sheet of Comparative Example 5 was obtained in the same manner as in Example 1.

[0439] (Performance evaluation, evaluation results)

[0440] For the decorative sheets of Examples 1 to 11 and Comparative Examples 1 to 5, the following were evaluated: “haze of the transparent resin layer (%)”, “pencil hardness”, “Hoffman scratch test”, “extrusion suitability”, and “bending whitening”. The methods described below were used as evaluation methods.

[0441] <Haze of the transparent resin layer (%)>

[0442] The haze (%) of the transparent resin layer was determined using a UV-Vis-NIR spectrophotometer (manufacturer: Shimadzu Corporation, model: UV-3600).

[0443] A resin with the same transparent resin layer composition as that of each embodiment / comparative example was extruded in a range of 70 [μm] to 80 [μm] to obtain a resin film. The haze was measured at a wavelength of 555 [nm] using a spectrophotometer (integrating sphere), and the haze was evaluated. Then, cases with haze less than 15% were evaluated as "◎", cases with haze between 15% and 25% were evaluated as "○", and cases with haze of 25% or more were evaluated as "×".

[0444] It should be noted that in this embodiment, "◎" and "○" are set as qualified.

[0445] <Pencil Hardness>

[0446] The pencil hardness was determined by an automatic pencil hardness tester (manufacturer: Jiman Precision Machinery, model: C221A).

[0447] After performing a pencil hardness test on the decorative materials of the decorative sheets containing each example / comparative example using pencils of different hardnesses, the damage (depressions) generated on the surface (surface protective layer) were confirmed, and the surface hardness was evaluated. Then, the case where damage occurred on the surface after performing the pencil hardness test using a pencil with a hardness of 2B or more was evaluated as "◎", and the case where damage occurred on the surface after performing the pencil hardness test using a pencil with a hardness of 4B or more was evaluated as "○". In addition, the case where damage occurred on the surface after performing the pencil hardness test using a pencil with a hardness of 5B or less was evaluated as "×".

[0448] It should be noted that in this example, "◎" and "○" were regarded as qualified.

[0449] <Hoffman Scratch Test>

[0450] The Hoffman scratch test was carried out as follows: A scratching blade (a cylindrical blade with a diameter of Φ7) was set to contact the surface of the decorative sheet at an angle of 45 degrees, and the testing machine was moved on the decorative sheet.

[0451] Scratches were generated by gradually increasing the load (heavy object) within the range of 200 - 2000 g (increments of 200 g each), and the load (g) at which damage occurred on the surface of the sample was evaluated. It should be noted that in the case where damage occurred at a load of 800 g, "600 g" was recorded as the tolerance load in the table.

[0452] It should be noted that in this example, the case where the tolerance load was "200 g" was regarded as unqualified.

[0453] <Extrusion Suitability>

[0454] The transparent resin layer was subjected to extrusion molding, and its production suitability (extrusion suitability) was confirmed.

[0455] As a result, if it could be manufactured (formed) without problems, it was set as "〇" (qualified). On the other hand, the case where defects might occur was set as "△" (unqualified).

[0456] <Bending Whitening>

[0457] The V-cutting processing suitability (presence or absence of bending whitening) was confirmed using the decorative sheet (i.e., decorative material) pasted on MDF.

[0458] As a result, the case where no whitening occurred was set as "○" (qualified), the case where slight whitening occurred was set as "△" (qualified), and the case where whitening occurred was set as "×" (unqualified).

[0459]

[0460]

[0461] The results of evaluating various performance parameters using the above method show that the decorative sheets of Examples 1 to 11 exhibited excellent performance in all evaluation tests. On the other hand, the decorative sheets of Comparative Examples 1 to 5 showed insufficient performance in at least some of the evaluation tests.

[0462] (Sixth implementation)

[0463] The following is for reference Figure 1 The composition of decorative material 10 is explained.

[0464] like Figure 1 As shown, the decorative material 10 comprises a decorative piece 1 and a substrate 9. It should be noted that the specific composition of the decorative piece 1 will be described later.

[0465] It should be noted that the composition of the decorative material 10 in the sixth embodiment is the same as that in the first embodiment, except for the composition of the decorative piece 1. Therefore, the description of the composition other than the decorative piece 1 is omitted.

[0466] (Composition of decorative pieces)

[0467] like Figure 1 As shown, the decorative piece 1 has a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface protective layer 6, a raised and recessed portion 7, and a primer layer 8.

[0468] <Colored substrate layer>

[0469] The colored substrate layer 2 is a resin layer formed using thermoplastic resin, which is a colored resin layer formed from a resin composition containing polyethylene derived from biomass (from plants).

[0470] The composition of the colored substrate layer 2 will be described in detail below.

[0471] (Polyethylene derived from biomass)

[0472] In the sixth embodiment, the polyethylene derived from biomass is polymerized from monomers containing ethylene derived from biomass. There is no particular limitation on the ethylene derived from biomass; ethylene produced by conventionally known methods can be used. Since ethylene derived from biomass is used as the monomer source, the polymerized polyethylene is derived from biomass.

[0473] It should be noted that the raw material monomers of polyethylene may not contain 100% by mass ethylene derived from biomass.

[0474] The monomers used as raw materials for polyethylene derived from biomass may further contain at least one of ethylene derived from fossil fuels and α-olefins derived from fossil fuels, or may further contain α-olefins derived from biomass.

[0475] There is no particular limitation on the number of carbon atoms in the aforementioned α-olefins; α-olefins with 3 to 20 carbon atoms are generally used, with butene, hexene, or octene being preferred. This is because butene, hexene, or octene can be manufactured by polymerizing ethylene, which is a feedstock derived from biomass. Furthermore, by containing such α-olefins, the polymerized polyethylene has an alkyl group as a branched structure, thus making it more flexible than simple linear polyethylene.

[0476] By using ethylene as a feedstock from biomass, it is theoretically possible to produce it from 100% biomass components.

[0477] The ethylene concentration from biomass in the aforementioned polyethylene (hereinafter sometimes referred to as "biomass content") is a value obtained by measuring the carbon content from biomass using radiocarbon (C14) determination. It is known that atmospheric carbon dioxide contains a certain proportion (105.5 pMC) of C14; therefore, the C14 content in plants that absorb atmospheric carbon dioxide (e.g., corn) is also approximately 105.5 pMC. Furthermore, it is known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in polyethylene, the proportion of carbon from biomass can be calculated. In the sixth embodiment, the C14 content in polyethylene is set as P. C14 Carbon content from biomass at that time P bio It can be calculated as follows.

[0478] P bio (%)=P C14 / 105.5×100

[0479] In the sixth embodiment, theoretically, if all ethylene from biomass is used as the raw material for polyethylene, the concentration of ethylene from biomass is 100%, and the biomass degree of the polyethylene from biomass is 100. Furthermore, in fossil fuel polyethylene manufactured solely from fossil fuel raw materials, the concentration of ethylene from biomass is 0%, and the biomass degree of the polyethylene from fossil fuels is 0.

[0480] In the sixth embodiment, the polyethylene derived from biomass or the decorative sheet containing such polyethylene does not require a biomass content of 100.

[0481] In the sixth embodiment, the polymerization method for monomers containing ethylene derived from biomass is not particularly limited, and can be carried out using conventionally known methods. The polymerization temperature and polymerization pressure can be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and conventionally known apparatus can be used. Hereinafter, an example of a polymerization method for monomers containing ethylene will be described.

[0482] The polymerization method for ethylene polymers or copolymers of ethylene and α-olefins can be appropriately selected based on the type of target polyethylene, such as the density or branching of high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). For example, it is preferable to use multi-site catalysts such as Ziegler-Natta catalysts or single-site catalysts such as metallocene catalysts as polymerization catalysts, and to carry out the polymerization in one or more stages using any of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[0483] In addition, polyethylene derived from biomass can be a polymer of ethylene alone or a copolymer of ethylene and α-olefins, or a mixture of two or more.

[0484] (A resin composition containing polyethylene derived from biomass)

[0485] In the sixth embodiment, the resin composition contains the aforementioned polyethylene as a main component. The resin composition contains at least 5% by mass, preferably 5 to 95% by mass, and more preferably 25 to 75% by mass of ethylene derived from biomass relative to the total resin composition. If the concentration of ethylene derived from biomass in the resin composition is 5% by mass or more, the amount of fossil fuel used can be reduced compared to conventional methods, enabling the achievement of carbon-neutral decorative sheets.

[0486] The above-mentioned resin composition may contain two or more types of polyethylene with different biomass concentrations, as long as the concentration of ethylene from biomass as a whole is within the above-mentioned range.

[0487] The resin composition described above may further comprise polyethylene derived from fossil fuels, which is obtained by polymerizing a monomer comprising at least one of ethylene and α-olefins derived from fossil fuels, and ethylene derived from fossil fuels. That is, in the sixth embodiment, the resin composition may also be a mixture of polyethylene derived from biomass and polyethylene derived from fossil fuels. The mixing method is not particularly limited, and conventionally known methods can be used. For example, dry blending or melt blending may be employed.

[0488] According to the sixth embodiment, the resin composition contains preferably 5 to 90% by mass, more preferably 25 to 75% by mass, of polyethylene derived from biomass; and preferably 10 to 95% by mass, more preferably 25 to 75% by mass, of polyethylene derived from fossil fuels. Even when using a resin composition with such a mixture, as long as the concentration of ethylene derived from biomass as a whole is within the above-mentioned range, it is acceptable.

[0489] In the resin composition manufactured in the above-described resin composition manufacturing process, various additives may be added in addition to polyethylene as the main component, without impairing its properties. Examples of additives include plasticizers, UV stabilizers, anti-staining agents, matting agents, deodorizers, flame retardants, weathering agents, antistatic agents, yarn friction reducers, slip agents, anti-sticking agents, antioxidants, ion exchangers, and coloring pigments. These additives are preferably added in the range of 1 to 20% by mass, more preferably 1 to 10% by mass, relative to the total resin composition.

[0490] As described above, the coloring substrate layer 2 contains ethylene derived from biomass at a concentration of 5% or more by mass relative to the total amount of the coloring substrate layer 2, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass. If the concentration of ethylene derived from biomass in the coloring substrate layer 2 is 5% or more by mass, the amount of fossil fuel used can be reduced compared to the past, and a carbon-neutral decorative sheet can be achieved.

[0491] The colored substrate layer 2 has a density of 0.92 g / cm³. 3 The above is 1.12 g / cm³ 3 Within the range below, preferably 0.98 g / cm³ 3 The above 1.10 [g / cm] 3 The density is within the range below. The density of the colored substrate layer 2 is determined by method A specified in JIS K7112-1980 after annealing as described in JIS K6760-1995. If the density of the colored substrate layer 2 is 0.92 g / cm³, the density is determined by the following method. 3 The above can improve the rigidity of the colored substrate layer 2. Additionally, if the density of the colored substrate layer 2 is 1.12 g / cm³, the rigidity of the substrate layer 2 can be improved. 3 The following steps can improve the transparency and mechanical strength of the colored substrate layer 2.

[0492] In the colored substrate layer 2, the polyethylene derived from biomass can be any of the following: polyethylene containing both high-density polyethylene and low-density polyethylene derived from biomass; polyethylene containing both high-density polyethylene derived from biomass and low-density polyethylene derived from fossil fuels; or polyethylene containing low-density polyethylene derived from biomass within high-density polyethylene derived from fossil fuels. The overall biomass content of the colored substrate layer 2 can be in the range of 10% to 90%.

[0493] It should be noted that high-density polyethylene derived from biomass refers to polyethylene with a density exceeding 0.94. Conversely, low-density polyethylene derived from biomass refers to polyethylene with a density below 0.94.

[0494] In the colored substrate layer 2, the polyethylene derived from biomass can be a blend of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) (which can be derived from either biomass or fossil fuels) in a ratio ranging from 95:5 to 70:30. When the content of LDPE is low, the film-forming stability is poor; when the content of LDPE is high, the film becomes too soft.

[0495] The manufacturing method of the colored substrate layer 2 is not particularly limited and can be manufactured by conventionally known methods. In the sixth embodiment, it is preferably formed by calendering.

[0496] Additionally, as needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers may be added to the colored substrate layer 2.

[0497] The thickness of the colored substrate layer 2 is preferably in the range of 40 μm to 200 μm, more preferably 51 μm to 120 μm, and even more preferably 55 μm to 100 μm. This is because when the thickness of the colored substrate layer 2, which is made of polyethylene derived from biomass, is 40 μm or more, it can absorb unevenness and steps in the flooring material or the like used as the substrate, thereby allowing for a good installation of the decorative sheet 1. Furthermore, when the thickness of the colored substrate layer 2 is 200 μm or less, a colored substrate layer 2 exceeding the required thickness will not be formed, thereby reducing the manufacturing cost of the decorative sheet 1.

[0498] It should be noted that in the sixth embodiment, polyethylene derived from biomass was described as the resin constituting the coloring substrate layer 2, but the present invention is not limited thereto. For example, polypropylene or polybutene derived from biomass may be used instead of the aforementioned polyethylene derived from biomass. That is, in the sixth embodiment, polyolefins derived from biomass can be widely used as the resin constituting the coloring substrate layer 2.

[0499] <Pattern Layer>

[0500] Pattern layer 3 is stacked on one side of colored substrate layer 2 (in) Figure 1 On the top side (the middle side), there is a layer for attaching patterns to give the design. It should be noted that if the coloring of the base material layer 2 can be used instead, the pattern layer 3 can also be omitted.

[0501] In addition, the pattern layer 3 is formed using printing inks or coatings. The printing inks or coatings that form the pattern layer 3 are formed, for example, by dissolving or dispersing colorants such as dyes or pigments together with a suitable binder resin in a suitable diluent.

[0502] The printing inks or coatings that form the pattern layer 3 are applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roller coating.

[0503] As an adhesive resin, for example, urethane resins, acrylic resins, vinyl chloroacetate resins, polyimide resins, nitrocellulose, or mixtures thereof can be used, but are not limited thereto.

[0504] As the pattern, any pattern can be used, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, text, symbols, single-color pigments, or combinations thereof. Furthermore, to improve the concealment of the decorative piece 1, a concealing layer can be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer can be formed, for example, using opaque printing inks or coatings containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0505] The thickness of the pattern layer 3 is preferably in the range of 1 μm to 10 μm. This is because when the thickness of the pattern layer 3 is 1 μm or more, the printing becomes clearer. In addition, when the thickness of the pattern layer 3 is 10 μm or less, the printability of the decorative sheet 1 is improved, and manufacturing costs can be reduced.

[0506] In addition, to impart various functions, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesives, desiccants, curing agents, curing accelerators, and curing delayers can be added to pattern layer 3.

[0507] Alternatively, the pattern layer 3 may be configured to have a solid-coated colored substrate layer to conceal the color / pattern of the base of the decorative piece 1, and a pattern layer for attaching a design-specific pattern.

[0508] <Adhesive Layer>

[0509] Adhesive layer 4 is stacked on one side of pattern layer 3 (in) Figure 1 On the top side (the middle side), there is a layer used to bond the pattern layer 3 and the transparent resin layer 5.

[0510] Materials used for adhesive layer 4 include, for example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, and polyolefin-based resins. In particular, considering adhesion to the transparent resin layer 5, polyolefin-based resins are preferred.

[0511] <Transparent resin layer>

[0512] The transparent resin layer 5 is stacked on one side of the adhesive layer 4 (in Figure 1 On the upper side (the middle side), there is a transparent resin layer formed of a resin composition containing the aforementioned polyethylene derived from biomass (from plants). More specifically, the transparent resin layer 5 is a resin layer formed of a resin composition containing polyethylene derived from biomass, which is polymerized from monomers containing ethylene derived from biomass. That is, in the transparent resin layer 5, a resin composition containing polyethylene derived from biomass used in the colored substrate layer 2 may also be used. In addition, it may contain polyethylene derived from fossil fuels, which is polymerized from monomers containing at least one of ethylene derived from fossil fuels and α-olefins, and ethylene derived from fossil fuels.

[0513] The transparent resin layer 5 may contain ethylene derived from biomass at a concentration of 5% or more by mass relative to the total amount of the transparent resin layer 5, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass. If the concentration of ethylene derived from biomass in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the past, and a carbon-neutral decorative sheet can be achieved.

[0514] The density of the transparent resin layer 5 is 0.92 g / cm³. 3 Above 0.99 g / cm³ 3 Within the range below, preferably 0.94 g / cm³ 3 Above 0.98 g / cm³3 Within the range below, more preferably 0.95 g / cm³ 3 Above 0.97 g / cm³ 3 The density is within the range below. The density of the transparent resin layer 5 is determined by method A specified in JIS K7112-1980 after annealing as described in JIS K6760-1995. If the density of the transparent resin layer 5 is 0.92 g / cm³... 3 The above can improve the rigidity of the transparent resin layer 5. Additionally, if the density of the transparent resin layer 5 is 0.99 g / cm³, the rigidity can be increased. 3 The following steps can improve the transparency and mechanical strength of the transparent resin layer 5.

[0515] The transparent resin layer 5 has a thickness of 55-150 μm, preferably 55-100 μm, and more preferably 60-80 μm.

[0516] The transparent resin layer 5 may contain high-density polyethylene derived from biomass as the biomass-derived polyethylene.

[0517] In addition, the transparent resin layer 5 may contain polyethylene derived from biomass, which is a blend of high-density polyethylene from biomass and low-density polyethylene from biomass in the range of 100:0 to 20:80.

[0518] In addition, the overall biomass content of the transparent resin layer 5 can be in the range of 10% to 90%.

[0519] The manufacturing method of the transparent resin layer 5 is not particularly limited and can be manufactured by conventionally known methods. In the sixth embodiment, it is preferably formed by extrusion molding, and more preferably by T-die molding or blow molding.

[0520] In the sixth embodiment, the transparent resin layer 5 and the colored substrate layer 2 preferably satisfy the following specific relationships regarding density, thickness, and biomass density (ethylene concentration from biomass).

[0521] In the sixth embodiment, the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 preferably satisfy d2>d1. This is because formability is required for the transparent resin layer 5 to function, and productivity is required for the colored substrate layer 2 to function.

[0522] It should be noted that the ratio (d2 / d1) of the density d1 of the transparent resin layer 5 to the density d2 of the colored substrate layer 2 is preferably in the range of 1.1 to 1.5, more preferably in the range of 1.1 to 1.3, and even more preferably in the range of 1.1 to 1.2. By ensuring that the density ratio of the transparent resin layer to the colored substrate layer is within this range, even when using polyethylene derived from biomass, it can possess the extrusion suitability and bending processing suitability required for decorative sheets.

[0523] In the sixth embodiment, the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored substrate layer 2 preferably satisfy t1 ≥ t2. This is because a thickness is required for the transparent resin layer 5 to function, but a thickness similar to that of the transparent resin layer 5 is not required for the colored substrate layer 2 to function.

[0524] It should be noted that the ratio (t1 / t2) of the thickness t1 of the transparent resin layer 5 to the thickness t2 of the colored substrate layer 2 is preferably in the range of 1.1 to 3, more preferably in the range of 1.1 to 2, and even more preferably in the range of 1.1 to 1.5.

[0525] In the sixth embodiment, the ethylene concentration C1 from biomass in the transparent resin layer 5 and the ethylene concentration C2 from biomass in the colored substrate layer 2 preferably satisfy C1 > C2. This is because, since the transparent resin layer 5 is thick and uses a large amount of ethylene in order to function as a transparent resin layer 5, the amount of fossil fuel used can be further reduced by increasing the biomass content of the transparent resin layer 5.

[0526] Nucleating agents (e.g., "Rikemaster CN-002" manufactured by RichenVitamin Co., Ltd.) may also be added to the biomass-derived polyethylene that forms the transparent resin layer 5.

[0527] Based on the mass of polyethylene, the nucleating agent is preferably added to polyethylene in the range of 500 to 2000 ppm, and more preferably in the range of 1500 to 2000 ppm.

[0528] As needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers can be added to the transparent resin layer 5.

[0529] It should be noted that the transparent resin layer 5 preferably has a degree of transparency (colorless transparent, colored transparent, semi-transparent) that allows the pattern of the pattern layer 3 to be seen through the surface (top) of the decorative sheet 1.

[0530] It should be noted that in the sixth embodiment, polyethylene derived from biomass was described as the biomass-derived resin constituting the transparent resin layer 5, but the present invention is not limited thereto. For example, polypropylene or polybutene derived from biomass may be used instead of the aforementioned biomass-derived polyethylene. That is, in the sixth embodiment, polyolefins derived from biomass can be widely used as the biomass-derived resin constituting the transparent resin layer 5.

[0531] <Surface Protective Layer>

[0532] Surface protective layer 6 is stacked on one side of transparent resin layer 5 (in) Figure 1 The middle (upper side) is a layer designed to give decorative piece 1 functions such as weather resistance, damage resistance, stain resistance, and design.

[0533] The surface protective layer 6 is formed of a resin composition containing at least a polyol, an isocyanate compound, and a hydroxyl (meth)acrylate, namely, urethane (meth)acrylate. Furthermore, in the surface protective layer 6, at least one of the polyol, isocyanate compound, or hydroxyl (meth)acrylate constituting the aforementioned urethane (meth)acrylate contains a component derived from biomass. That is, the surface protective layer 6 contains a component derived from biomass. At least any one of the polyol, isocyanate compound, or hydroxyl (meth)acrylate may or may not contain a component derived from biomass. In the following description, urethane (meth)acrylate containing a component derived from biomass is also referred to as bio-urethane (meth)acrylate.

[0534] Carbamate (meth)acrylates are obtained, for example, by reacting a polyol and an isocyanate with a hydroxyl ester of (meth)acrylate. In bio-carbamate (meth)acrylates, the polyol can be a plant-derived polyol, and the isocyanate can be a plant-derived isocyanate, or both the polyol and the isocyanate can be plant-derived substances.

[0535] As polyols, the following can be used: polyester polyols as reaction products of polyfunctional alcohols and polyfunctional carboxylic acids, polyether polyols as reaction products of polyfunctional alcohols and polyfunctional isocyanates, or polycarbonate polyols as reaction products of polyfunctional alcohols and carbonates. The following describes each polyol.

[0536] <Polyester Polyols>

[0537] When a polyester polyol contains components derived from biomass, at least one of the polyfunctional alcohols and polyfunctional carboxylic acids contains components derived from biomass. Examples of polyester polyols containing components derived from biomass include the following.

[0538] • Reaction products of polyfunctional alcohols and polyfunctional carboxylic acids derived from biomass

[0539] • Reaction products of polyfunctional alcohols from fossil fuels and polyfunctional carboxylic acids from biomass

[0540] • Reaction products of polyfunctional alcohols from biomass and polyfunctional carboxylic acids from fossil fuels

[0541] Aliphatic polyfunctional alcohols derived from biomass can be used from plant sources such as corn, sugarcane, cassava, and sago palm. Examples of aliphatic polyfunctional alcohols derived from biomass include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), and hexamethylene glycol, all obtained from plant sources through the methods described below. These can be used alone or in combination.

[0542] Polypropylene glycol derived from biomass is produced by fermentation, which breaks down plant materials to obtain glucose, and by using glycerol via 3-hydroxypropionaldehyde (HPA). Compared to polypropylene glycol produced by the EO manufacturing method, polypropylene glycol produced by this bio-based fermentation method is preferred because it yields useful byproducts such as lactic acid from a safety perspective and also keeps manufacturing costs lower.

[0543] Butanediol derived from biomass can be produced by manufacturing diols from plant materials, fermenting them to obtain succinic acid, and then hydrogenating it.

[0544] Ethylene glycol derived from biomass can be produced, for example, from bioethanol obtained by conventional methods via ethylene.

[0545] As a polyfunctional alcohol derived from fossil fuels, compounds having two or more hydroxyl groups, preferably two to eight, per molecule can be used. Specifically, there are no particular limitations on the polyfunctional alcohol derived from fossil fuels; conventionally known substances can be used, such as, in addition to polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butanediol (BG), and hexamethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, trimethylolpropane, glycerol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, etc. These can be used alone or in combination of two or more.

[0546] As biomass-derived polyfunctional carboxylic acids, aliphatic polyfunctional carboxylic acids can be obtained from plant-based raw materials such as reproducible soybean oil, linseed oil, tung oil, coconut oil, palm oil, castor oil, etc., as well as recycled oils obtained from the recycling of waste edible oils mainly composed of these. Examples of biomass-derived aliphatic polyfunctional carboxylic acids include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acids. For example, sebacic acid is generated by the acid-base thermal decomposition of castor oil obtained from castor oil, with heptanol as a byproduct. In this invention, succinic acid or sebacic acid derived from biomass is particularly preferred. These can be used alone or in combination of two or more.

[0547] As polyfunctional carboxylic acids derived from fossil fuels, aliphatic or aromatic polyfunctional carboxylic acids can be used. For aliphatic polyfunctional carboxylic acids derived from fossil fuels, there are no particular limitations; conventionally known substances can be used, such as adipic acid, dodecanoic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acids, and their ester compounds. Similarly, for aromatic polyfunctional carboxylic acids derived from fossil fuels, there are no particular limitations; conventionally known substances can be used, such as isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, and their ester compounds. These can be used alone or in combination of two or more.

[0548] <Polyether polyols>

[0549] When a polyether polyol contains a component derived from biomass, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains a component derived from biomass. Examples of polyether polyols containing a component derived from biomass include the following.

[0550] • Reaction products of biomass-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates

[0551] • Reaction products of polyfunctional alcohols derived from fossil fuels and polyfunctional isocyanates derived from biomass

[0552] As polyfunctional alcohols derived from biomass and polyfunctional alcohols derived from fossil fuels, the polyfunctional alcohols derived from biomass and polyfunctional alcohols derived from fossil fuels described above in the section on polyester polyols can be used.

[0553] As a polyfunctional isocyanate derived from biomass, it can be obtained by amidation and reduction of a dicarboxylic acid from a plant to a terminal amino group, followed by reaction with phosgene to convert the amino group into an isocyanate group. Examples of biomass-derived polyfunctional isocyanates include biomass-derived diisocyanates. Examples of biomass-derived diisocyanates include dimer diisocyanate (DDI), octamethylene diisocyanate, and decamethylene diisocyanate. Alternatively, plant-derived diisocyanates can be obtained by using amino acids from plants as raw materials and converting the amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by esterifying the carboxyl methyl group of lysine to convert the amino group into an isocyanate group. Furthermore, 1,5-pentamethylene diisocyanate is obtained by decarboxylating the carboxyl group of lysine to convert the amino group into an isocyanate group.

[0554] Other methods for synthesizing 1,5-pentamethylene diisocyanate include phosgenation and carbamate esterification. More specifically, phosgenation involves reacting 1,5-pentamethylenediamine or its salt directly with phosgene, or suspending pentamethylenediamine hydrochloride in an inert solvent and reacting it with phosgene to synthesize 1,5-pentamethylenediisocyanate. Carbamate esterification involves first carbamateing 1,5-pentamethylenediamine or its salt to generate pentamethylenedicarbamate (PDC), and then synthesizing 1,5-pentamethylenediisocyanate through thermal decomposition. In this invention, a preferred polyisocyanate is the 1,5-pentamethylenediisocyanate-based polyisocyanate manufactured by Mitsui Chemicals Co., Ltd. (trade name: STABiO (registered trademark)).

[0555] As a polyfunctional isocyanate derived from fossil fuels, there are no particular limitations, and conventionally known substances can be used, such as: toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylenebis(phenylene isocyanate) (MDI), dextrin diisocyanate, benzyl diisocyanate, phenyl dimethyl diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-dibenzyl diisocyanate, and other aromatic diisocyanates. In addition, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate can be listed; alicyclic diisocyanates such as 1,4-cyclohexylene diisocyanate, 4,4-methylenebis(cyclohexyl)isocyanate, 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI can also be listed. These can be used alone or in combination of two or more.

[0556] <Polycarbonate polyols>

[0557] When polycarbonate polyols contain components derived from biomass, the reaction product of a polyfunctional alcohol containing components derived from biomass and a carbonate derived from fossil fuels can be used as the polycarbonate polyol. Alternatively, the reaction product of a polyfunctional alcohol containing components derived from fossil fuels and a carbonate derived from biomass can be used. Examples of carbonates include dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, and diphenyl carbonate. They can be used alone or in combination of two or more.

[0558] As a biomass-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol described in the above-mentioned polyester polyols can be used.

[0559] <Isocyanate compounds>

[0560] Next, the isocyanate compound will be described. As an isocyanate compound containing components derived from biomass, a biomass-derived polyfunctional isocyanate as described in the section on polyether polyols can be used.

[0561] Hydroxyl (meth)acrylate

[0562] Next, hydroxy methacrylates will be described. Examples of hydroxy methacrylates include: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and 2-hydroxy-3-phenoxypropyl methacrylate, which have one methacryloyl group; and hydroxy methacrylates with two or more methacryloyl groups, such as di(meth)acrylate, pentaerythritol tri(meth)acrylate, di(trimethylolpropane)tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and sorbitol penta(meth)acrylate. These can be used individually or in combination of two or more.

[0563] In addition to the aforementioned bio-carbamate (meth)acrylate, the surface protective layer 6 may also contain nitrocellulose. That is, the surface protective layer 6 can be formed from the aforementioned bio-carbamate (meth)acrylate, or it can be formed by adding nitrocellulose to the bio-carbamate (meth)acrylate.

[0564] Nitrocellulose

[0565] Nitrocellulose is a nitro-substituted cellulose resin formed by nitrifying a portion of the hydroxyl groups in the cellulose backbone. The cellulose backbone of nitrocellulose resin is a biomass material. As nitrocellulose, ordinary nitrocellulose can be used without hindrance, but nitrocellulose formed by replacing each glucose unit constituting the cellulose backbone with an average of 1.3 to 2.7 nitro groups is particularly preferred.

[0566] Nitrocellulose exists in L-form and H-form based on its molecular weight. Considering its solubility in organic solvents, the L-form is preferred.

[0567] The surface protective layer 6 preferably has a biomass content of 5% or more, more preferably 5% or more and 50% or less, and even more preferably 10% or more and 50% or less. If the biomass content is within the above range, the amount of fossil fuel used can be reduced, thereby reducing the environmental impact. The dried weight of the surface protective layer 6 is preferably 0.1 g / m³. 2 ]Above 15 [g / m 2 The following, or more preferably, is 3 g / m 2 ]Above 10 [g / m 2 The following, and more preferably 6 g / m 2 Above 9 [g / m 2 The surface protective layer 6 preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 3 μm or more and 10 μm or less, and even more preferably 6 μm or more and 9 μm or less.

[0568] Regarding "biomass content", for example in the case of biocarbamate (meth)acrylate, as described above, it is determined as a value for the carbon content from biomass measured using radiocarbon (C14) determination.

[0569] Furthermore, regarding "biomass content," for example, in the case of nitrocellulose, since each glucose unit (formula = 172) constituting the cellulose backbone as the starting material contains 3 hydroxyl groups, 1 to 3 of these hydroxyl groups can undergo nitration (hydrogen is replaced by nitro groups (non-biomass material, formula = 46)). Thus, assuming the original cellulose backbone is composed of 100% by weight biomass material, and with an average of n nitro groups being replaced per glucose unit, the proportion (by weight) of biomass material in the total nitrocellulose molecule can be calculated using (172-n) × 100 / (172-n + 46n).

[0570] Regarding the proportion of biomass material in the overall nitrocellulose molecule, it is approximately 78.8% by weight when each glucose unit constituting the cellulose backbone is replaced by an average of one nitro group, approximately 64.9% by weight when replaced by two nitro groups, and approximately 55.0% by weight when replaced by three nitro groups (calculated values ​​in the above formula).

[0571] In addition, depending on the requirements, the surface protective layer 6 may contain various additives such as weather resistant agents, plasticizers, stabilizers, fillers, dispersants, dyes, pigments and other colorants, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst trapping agents, colorants, light scattering agents, and gloss modifiers. Furthermore, depending on the requirements, the surface protective layer 6 may also contain functional additives such as antibacterial agents and antifungal agents.

[0572] <Concave and convex parts>

[0573] The uneven portion 7 is formed by recesses provided at multiple locations in the transparent resin layer 5 and the surface protective layer 6.

[0574] <Primer layer>

[0575] The primer layer 8 is a base layer used to improve the adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9.

[0576] In addition, the primer layer 8 is laminated on the other side of the colored substrate layer 2 (in Figure 1 (The middle is the lower side surface).

[0577] In addition, the primer layer 8 is formed, for example, using polyester resin, organic additives, pigments, etc.

[0578] It should be noted that, in order to improve corrosion resistance, anti-rust pigments can be added to the primer layer 8.

[0579] The thickness of the primer layer 8 is, for example, in the range of 1 [μm] to 10 [μm].

[0580] It should be noted that the above-described embodiments are an example of the present invention. The present invention is not limited to the above-described embodiments. Even in ways other than those described, as long as they do not depart from the technical concept of the present invention, various changes can be made according to the design, etc.

[0581] (Effects of the sixth embodiment)

[0582] If it is the decorative piece 1 of the sixth embodiment, it can achieve the following effects.

[0583] (1) The colored substrate layer 2 and the transparent resin layer 5 are resin layers formed by resin compositions containing polyolefins from biomass, and the surface protective layer 6 contains components from biomass.

[0584] Therefore, it is possible to provide decorative sheets that reduce the use of fossil fuels by using materials derived from plants and that maintain physical properties suitable for use as decorative sheets.

[0585] (2) The surface protective layer 6 is a resin layer formed of a resin composition containing at least a polyol, an isocyanate compound and a (meth)acrylate hydroxy ester, namely urethane (meth)acrylate, wherein at least one of the polyol, isocyanate compound and (meth)acrylate hydroxy ester contained in the resin composition contains a component derived from biomass.

[0586] Therefore, it is possible to provide decorative sheets that can reliably reduce the use of fossil fuels by using materials derived from plants, and reliably maintain physical properties suitable for use as decorative sheets.

[0587] (3) The polyol that forms the bio-urethane (meth) acrylate of the surface protective layer 6 is a polyester polyol containing a component derived from biomass, a polyether polyol containing a component derived from biomass, or a polycarbonate polyol containing a component derived from biomass.

[0588] Therefore, it is possible to provide decorative sheets that can more reliably reduce the use of fossil fuels by using materials derived from plants, and can more reliably maintain the physical properties suitable for use as decorative sheets.

[0589] (4) The polyester polyols that are constituent elements of the above-mentioned bio-carbamate (meth)acrylates are either polyfunctional alcohols containing components from biomass and polyfunctional carboxylic acids containing components from fossil fuels, or polyfunctional alcohols containing components from fossil fuels and polyfunctional carboxylic acids containing components from biomass.

[0590] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0591] (5) The polyether polyols that are constituent elements of the above-mentioned bio-carbamate (meth)acrylates are reaction products of polyfunctional alcohols containing components from biomass and polyfunctional isocyanates containing components from fossil fuels, or reaction products of polyfunctional alcohols containing components from fossil fuels and polyfunctional isocyanates containing components from biomass.

[0592] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0593] (6) The polycarbonate polyols that are constituent elements of the above-mentioned bio-carbamate (meth)acrylates are either the reaction products of polyfunctional alcohols containing components from biomass and carbonates containing components from fossil fuels, or the reaction products of polyfunctional alcohols containing components from fossil fuels and carbonates containing components from biomass.

[0594] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0595] (7) The isocyanate compound that forms the bio-carbamate (meth)acrylate that forms the surface protective layer 6 is an isocyanate compound containing components derived from biomass.

[0596] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0597] (8) A decorative sheet 1 having a substrate 9 and a decorative sheet 1 laminated on at least one side of the substrate 9.

[0598] Therefore, it is possible to provide decorative materials that can reduce the use of fossil fuels by using materials derived from plants, while maintaining physical properties suitable for use as decorative panels.

[0599] Example 4

[0600] Hereinafter, the decorative materials of Examples 1 to 9 and the decorative materials of Examples 1 to 3 will be described with reference to the sixth embodiment.

[0601] (Example 1)

[0602] After applying corona discharge treatment to one side of the substrate, a pattern layer printed with urethane-based printing ink, a urethane-based adhesive layer, a maleic anhydride-modified polyethylene resin layer (transparent adhesive layer), a transparent resin layer, and a surface protective layer are sequentially layered on that side of the substrate. Furthermore, after applying corona discharge treatment to the other side of the substrate, a primer layer (thickness: 1–2 μm) composed of polyester urethane resin is formed. Thus, the decorative sheet of Example 1 (total thickness: 135 μm) is obtained.

[0603] In Example 1, a colored substrate layer (thickness: 55 μm) was used as the substrate, formed from a resin composition containing high-density polyethylene from biomass and low-density polyethylene from fossil fuels. The colored substrate layer was obtained by calendering this resin composition. The biomass content of the thus formed colored substrate layer was 80%, and the density of the colored substrate layer was 1.08 g / cm³. 3 ].

[0604] For the transparent resin layer, a transparent resin layer (thickness: 80 μm) is formed using a resin composition containing biomass-derived polyethylene (Braskem Corporation's "Biomass Polyethylene"). This biomass-derived polyethylene is a resin obtained by blending high-density polyethylene (SHC7260) and low-density polyethylene (SPB681) derived from biomass at a ratio (high-density polyethylene / low-density polyethylene) of 80 / 20. The transparent resin layer is obtained by extrusion lamination of this resin. The resulting transparent resin layer has a biomass content of 94% and a density of 0.95 g / cm³. 3 ].

[0605] The surface protective layer uses a bio-urethane (meth)acrylate, a reaction product of a polyester polyol containing components derived from biomass, an isocyanate compound from fossil fuels, and a (meth)acrylate hydroxyl ester from fossil fuels. The polyester polyol containing components derived from biomass is a polyester polyol that is a reaction product of a polyfunctional alcohol containing components derived from biomass and a polyfunctional carboxylic acid from fossil fuels.

[0606] (Example 2)

[0607] As the polyester polyol in the bio-urethane (meth) acrylate that forms the surface protective layer, the decorative sheet of Example 2 was obtained by using the reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional carboxylic acid containing components derived from biomass, in the same manner as in Example 1.

[0608] (Example 3)

[0609] As the bio-urethane (meth)acrylate forming the surface protective layer, the bio-urethane (meth)acrylate is a reaction product of a polyester polyol derived from fossil fuels, an isocyanate compound containing components derived from biomass, and a (meth)acrylate hydroxyl ester derived from fossil fuels. Otherwise, the decorative sheet of Example 3 was obtained in the same manner as in Example 1.

[0610] (Example 4)

[0611] As the polyol in the bio-urethane (meth)acrylate that forms the surface protective layer, a polyether polyol was used, and otherwise, the decorative sheet of Example 4 was obtained in the same manner as in Example 1. Specifically, as the polyether polyol, the reaction product of a polyfunctional alcohol containing components from biomass and a polyfunctional isocyanate from fossil fuels was used.

[0612] (Example 5)

[0613] As the polyether polyol in the bio-urethane (meth) acrylate that forms the surface protective layer, the decorative sheet of Example 5 was obtained by using the reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional isocyanate containing components derived from biomass, in the same manner as in Example 4.

[0614] (Example 6)

[0615] The polyol used in the bio-urethane (meth)acrylate that forms the surface protective layer is a polyether polyol derived from fossil fuels. Otherwise, the decorative sheet of Example 6 was obtained in the same manner as in Example 3.

[0616] (Example 7)

[0617] As the polyol in the bio-urethane (meth)acrylate that forms the surface protective layer, a polycarbonate polyol was used. Otherwise, the decorative sheet of Example 7 was obtained in the same manner as in Example 1. Specifically, as the polycarbonate polyol, a reaction product of a polyfunctional alcohol containing components from biomass and a carbonate from fossil fuels was used.

[0618] (Example 8)

[0619] As the polyol in the bio-urethane (meth)acrylate that forms the surface protective layer, a polycarbonate polyol derived from fossil fuels was used. Otherwise, the decorative sheet of Example 8 was obtained in the same manner as in Example 3.

[0620] (Example 9)

[0621] The polyethylene from biomass used for the transparent resin layer was a resin made by blending high-density polyethylene (SHC7260) from biomass and low-density polyethylene (SPB681) from biomass in a ratio (high-density polyethylene / low-density polyethylene) of 100 / 0. Otherwise, the decorative sheet of Example 9 was obtained in the same manner as in Example 1.

[0622] (See Example 1 for reference)

[0623] Except for the surface protective layer formed by the acrylic resin-based UV-curable resin, the decorative sheet of Reference Example 1 was obtained in the same manner as in Example 1.

[0624] (See Example 2 for reference)

[0625] Except that a transparent resin layer was obtained by extruding and laminating homopolymer polypropylene resin derived from fossil fuels produced by Prime Polymer Co., Ltd., the decorative sheet of Reference Example 2 was obtained in the same manner as in Example 1.

[0626] (See Example 3 for reference)

[0627] Except that the colored substrate layer was obtained using only colored polyethylene resin derived from fossil fuels, the decorative sheet of Reference Example 3 was obtained in the same manner as in Example 1.

[0628] (Performance evaluation, evaluation results)

[0629] For the decorative sheets of Examples 1 to 9 and the decorative sheets of Reference Examples 1 to 3, the following were evaluated: “haze of transparent resin layer (%)”, “pencil hardness”, “Hoffman scratch test”, “extrusion suitability”, and “bending whitening”. The following methods were used as the evaluation methods.

[0630] <Haze of the transparent resin layer (%)>

[0631] The haze (%) of the transparent resin layer was determined using a UV-Vis-NIR spectrophotometer (manufacturer: Shimadzu Corporation, model: UV-3600).

[0632] The resin having the same composition as the transparent resin layer of each of the examples / reference examples was extruded within the range of a thickness of 70 [μm] or more and 80 [μm] or less to obtain a resin film. The haze at a wavelength of 555 nm was measured using a spectrophotometer (integrating sphere), and the haze was evaluated. Then, a case where the haze was less than 15% was evaluated as "◎", a case where the haze was 15% or more and less than 25% was evaluated as "○", and a case where the haze was 25% or more was evaluated as "×".

[0633] It should be noted that in this example, "◎" and "○" were regarded as qualified.

[0634] <Pencil hardness>

[0635] The pencil hardness was measured using a pencil hardness tester (automatic) (manufacturer: Yoshimitsu Seiki Co., Ltd., model: C221A).

[0636] After performing a pencil hardness test on the decorative material including the decorative sheet of each of the examples / reference examples using pencils with different hardnesses, the damage (dents) generated on the surface (surface protective layer) was confirmed, and the surface hardness was evaluated. Then, a case where damage occurred on the surface after performing a pencil hardness test using a pencil with a hardness of 2B or more was evaluated as "◎", and a case where damage occurred on the surface after performing a pencil hardness test using a pencil with a hardness of 4B or more was evaluated as "○". In addition, a case where damage occurred on the surface after performing a pencil hardness test using a pencil with a hardness of 5B or less was evaluated as "×".

[0637] It should be noted that in this example, "◎" and "○" were regarded as qualified.

[0638] <Hoffman scratch test>

[0639] The Hoffman scratch test was performed as follows: A scratching blade (a cylindrical blade with a diameter of Φ7) was set to contact the surface of the decorative sheet at an angle of 45 degrees, and the testing machine was moved on the decorative sheet.

[0640] Scratches were generated by gradually increasing the load (heavy object) within the range of 200 to 2000 g (increments of 200 g each), and the load (g) at which damage occurred on the surface of the sample was evaluated. It should be noted that in the case where damage occurred at a load of 800 g, "600 g" was recorded as the tolerance load in the table.

[0641] It should be noted that in this example, a case where the tolerance load was "200 g" was regarded as unqualified.

[0642] <Extrusion suitability>

[0643] The transparent resin layer was subjected to extrusion molding, and its production suitability (extrusion suitability) was confirmed.

[0644] As a result, if the product can be manufactured (formed) without any problems, it is marked as "0" (qualified). On the other hand, situations where defects may occur are marked as "△" (unqualified).

[0645] <Bending Whitening>

[0646] Use the decorative sheet (i.e., decorative material) pasted on the MDF to confirm the suitability of V-cut processing (whether there is bending whitening).

[0647] As a result, cases without whitening were marked as "○" (pass), cases with slight whitening were marked as "△" (pass), and cases with whitening were marked as "×" (fail).

[0648]

[0649]

[0650] The results of evaluating various properties using the above methods show that the decorative sheets of Examples 1 to 9 exhibited superior performance, equivalent to or better than that of Reference Examples 1-3, in all evaluation tests. That is, it can be seen that the decorative sheets of Examples 1 to 9, by using materials derived from plants, can reduce the use of fossil fuels and maintain physical properties suitable for use as decorative sheets.

[0651] (Seventh implementation)

[0652] The following is for reference Figure 1 The composition of decorative material 10 is explained.

[0653] like Figure 1 As shown, the decorative material 10 comprises a decorative piece 1 and a substrate 9. It should be noted that the specific composition of the decorative piece 1 will be described later.

[0654] It should be noted that the composition of the decorative material 10 in the seventh embodiment is the same as that in the first embodiment, except for the composition of the decorative piece 1. Therefore, the description of the composition other than the decorative piece 1 is omitted.

[0655] (Composition of decorative pieces)

[0656] like Figure 1 As shown, the decorative piece 1 has a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface protective layer 6, a raised and recessed portion 7, and a primer layer 8.

[0657] <Colored substrate layer>

[0658] The colored substrate layer 2 is a resin layer formed using thermoplastic resin, which is a colored resin layer formed from a resin composition containing polyethylene derived from biomass (from plants).

[0659] The composition of the colored substrate layer 2 will be described in detail below.

[0660] (Polyethylene derived from biomass)

[0661] In the seventh embodiment, the polyethylene derived from biomass is polymerized from monomers containing ethylene derived from biomass. There is no particular limitation on the ethylene derived from biomass; ethylene produced by conventionally known methods can be used. Since ethylene derived from biomass is used as the monomer source, the polymerized polyethylene is derived from biomass.

[0662] It should be noted that the raw material monomers of polyethylene may not contain 100% by mass ethylene derived from biomass.

[0663] The monomers used as raw materials for polyethylene derived from biomass may further contain at least one of ethylene derived from fossil fuels and α-olefins derived from fossil fuels, or may further contain α-olefins derived from biomass.

[0664] There is no particular limitation on the number of carbon atoms in the aforementioned α-olefins; α-olefins with 3 to 20 carbon atoms are generally used, with butene, hexene, or octene being preferred. This is because butene, hexene, or octene can be manufactured by polymerizing ethylene, which is a feedstock derived from biomass. Furthermore, by containing such α-olefins, the polymerized polyethylene has an alkyl group as a branched structure, thus making it more flexible than simple linear polyethylene.

[0665] By using ethylene as a feedstock from biomass, it is theoretically possible to produce it from 100% biomass components.

[0666] The ethylene concentration derived from biomass in the aforementioned polyethylene (hereinafter sometimes referred to as "biomass content") is a value obtained by measuring the carbon content derived from biomass using radiocarbon (C14) determination. It is known that atmospheric carbon dioxide contains a certain proportion (105.5 pMC) of C14; therefore, the C14 content in plants that absorb atmospheric carbon dioxide (e.g., corn) is also approximately 105.5 pMC. Furthermore, it is known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in polyethylene, the proportion of carbon derived from biomass can be calculated. In the seventh embodiment, the C14 content in polyethylene is set as P. C14 Carbon content from biomass at that time P bio It can be calculated as follows.

[0667] P bio (%)=P C14 / 105.5×100

[0668] In the seventh embodiment, theoretically, if all ethylene from biomass is used as the raw material for polyethylene, the concentration of ethylene from biomass is 100%, and the biomass degree of the polyethylene from biomass is 100. Furthermore, in fossil fuel polyethylene manufactured solely from fossil fuel raw materials, the concentration of ethylene from biomass is 0%, and the biomass degree of the polyethylene from fossil fuels is 0.

[0669] In the seventh embodiment, the polyethylene derived from biomass or the decorative sheet containing such polyethylene does not require a biomass content of 100.

[0670] In the seventh embodiment, the polymerization method for monomers containing ethylene derived from biomass is not particularly limited, and can be carried out using conventionally known methods. The polymerization temperature and polymerization pressure can be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and conventionally known apparatus can be used. Hereinafter, an example of a polymerization method for monomers containing ethylene will be described.

[0671] The polymerization method for ethylene polymers or copolymers of ethylene and α-olefins can be appropriately selected based on the type of target polyethylene, such as the density or branching of high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). For example, it is preferable to use multi-site catalysts such as Ziegler-Natta catalysts or single-site catalysts such as metallocene catalysts as polymerization catalysts, and to carry out the polymerization in one or more stages using any of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[0672] In addition, polyethylene derived from biomass can be a polymer of ethylene alone or a copolymer of ethylene and α-olefins, or a mixture of two or more.

[0673] (A resin composition containing polyethylene derived from biomass)

[0674] In the seventh embodiment, the resin composition contains the aforementioned polyethylene as a main component. The resin composition contains at least 5% by mass, preferably 5 to 95% by mass, and more preferably 25 to 75% by mass of ethylene derived from biomass relative to the total resin composition. If the concentration of ethylene derived from biomass in the resin composition is 5% by mass or more, the amount of fossil fuel used can be reduced compared to conventional methods, enabling the achievement of carbon-neutral decorative sheets.

[0675] The above-mentioned resin composition may contain two or more types of polyethylene with different biomass concentrations, as long as the concentration of ethylene from biomass as a whole is within the above-mentioned range.

[0676] The resin composition described above may further comprise polyethylene derived from fossil fuels, which is obtained by polymerizing a monomer comprising at least one of ethylene and α-olefins derived from fossil fuels, and ethylene derived from fossil fuels. That is, in embodiment 7, the resin composition may also be a mixture of polyethylene derived from biomass and polyethylene derived from fossil fuels. The mixing method is not particularly limited, and conventionally known methods can be used. For example, dry blending or melt blending may be employed.

[0677] According to the seventh embodiment, the resin composition contains preferably 5 to 90% by mass, more preferably 25 to 75% by mass, of polyethylene derived from biomass; and preferably 10 to 95% by mass, more preferably 25 to 75% by mass, of polyethylene derived from fossil fuels. Even when using a resin composition with such a mixture, as long as the concentration of ethylene derived from biomass as a whole is within the above-mentioned range, it is acceptable.

[0678] In the resin composition manufactured in the above-described resin composition manufacturing process, various additives may be added in addition to polyethylene as the main component, without impairing its properties. Examples of additives include plasticizers, UV stabilizers, anti-staining agents, matting agents, deodorizers, flame retardants, weathering agents, antistatic agents, yarn friction reducers, slip agents, anti-sticking agents, antioxidants, ion exchangers, and coloring pigments. These additives are preferably added in the range of 1 to 20% by mass, more preferably 1 to 10% by mass, relative to the total resin composition.

[0679] As described above, the coloring substrate layer 2 contains ethylene derived from biomass at a concentration of 5% or more by mass relative to the total amount of the coloring substrate layer 2, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass. If the concentration of ethylene derived from biomass in the coloring substrate layer 2 is 5% or more by mass, the amount of fossil fuel used can be reduced compared to the past, and a carbon-neutral decorative sheet can be achieved.

[0680] The colored substrate layer 2 has a density of 0.92 g / cm³. 3 The above is 1.12 g / cm³ 3 Within the range below, preferably 0.98 g / cm³ 3 The above 1.10 [g / cm] 3The density is within the range below. The density of the colored substrate layer 2 is determined by method A specified in JIS K7112-1980 after annealing as described in JIS K6760-1995. If the density of the colored substrate layer 2 is 0.92 g / cm³, the density is determined by the following method. 3 The above can improve the rigidity of the colored substrate layer 2. Additionally, if the density of the colored substrate layer 2 is 1.12 g / cm³, the rigidity of the substrate layer 2 can be improved. 3 The following steps can improve the transparency and mechanical strength of the colored substrate layer 2.

[0681] In the colored substrate layer 2, the polyethylene derived from biomass can be any of the following: polyethylene containing both high-density polyethylene and low-density polyethylene derived from biomass; polyethylene containing both high-density polyethylene derived from biomass and low-density polyethylene derived from fossil fuels; or polyethylene containing low-density polyethylene derived from biomass within high-density polyethylene derived from fossil fuels. The overall biomass content of the colored substrate layer 2 can be in the range of 10% to 90%.

[0682] It should be noted that high-density polyethylene derived from biomass refers to polyethylene with a density exceeding 0.94. Conversely, low-density polyethylene derived from biomass refers to polyethylene with a density below 0.94.

[0683] In the colored substrate layer 2, the polyethylene derived from biomass can be a blend of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) (which can be derived from either biomass or fossil fuels) in a ratio ranging from 95:5 to 70:30. When the content of LDPE is low, the film-forming stability is poor; when the content of LDPE is high, the film becomes too soft.

[0684] The manufacturing method of the colored substrate layer 2 is not particularly limited and can be manufactured by conventionally known methods. In the seventh embodiment, it is preferably formed by calendering.

[0685] Additionally, as needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers may be added to the colored substrate layer 2.

[0686] The thickness of the colored substrate layer 2 is preferably in the range of 40 μm to 200 μm, more preferably 51 μm to 120 μm, and even more preferably 55 μm to 100 μm. This is because when the thickness of the colored substrate layer 2, which is made of polyethylene derived from biomass, is 40 μm or more, it can absorb unevenness and steps in the flooring material or the like used as the substrate, thereby allowing for a good installation of the decorative sheet 1. Furthermore, when the thickness of the colored substrate layer 2 is 200 μm or less, a colored substrate layer 2 exceeding the required thickness will not be formed, thereby reducing the manufacturing cost of the decorative sheet 1.

[0687] It should be noted that in the seventh embodiment, polyethylene derived from biomass was described as the resin constituting the coloring substrate layer 2, but the present invention is not limited thereto. For example, polypropylene or polybutene derived from biomass may be used instead of the aforementioned polyethylene derived from biomass. That is, in the seventh embodiment, polyolefins derived from biomass can be widely used as the resin constituting the coloring substrate layer 2.

[0688] <Pattern Layer>

[0689] Pattern layer 3 is stacked on one side of colored substrate layer 2 (in) Figure 1 The top surface (the middle one) is used to attach layers for adding patterns to give the design.

[0690] In addition, the pattern layer 3 is formed using printing inks or coatings. The printing inks or coatings that form the pattern layer 3 are formed, for example, by dissolving or dispersing colorants such as dyes or pigments together with a suitable binder resin in a suitable diluent.

[0691] The printing inks or coatings that form the pattern layer 3 are applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roller coating.

[0692] The pattern layer 3 is formed by containing the aforementioned colorant and binder resin. Hereinafter, the binder resin used for the pattern layer 3 in the seventh embodiment will be described.

[0693] [Adhesive Resin]

[0694] The adhesive resin contained in pattern layer 3 comprises a resin composition containing at least a polyol, an isocyanate compound, and a (meth)acrylate hydroxyl ester, namely, urethane (meth)acrylate. Furthermore, in pattern layer 3, at least one of the polyol, isocyanate compound, or (meth)acrylate hydroxyl ester constituting the aforementioned urethane (meth)acrylate contains a component derived from biomass. At least any one of the polyol, isocyanate compound, or (meth)acrylate hydroxyl ester may or may not contain a component derived from biomass. In the following description, urethane (meth)acrylate containing a component derived from biomass is also referred to as bio-urethane (meth)acrylate.

[0695] That is, pattern layer 3 is a resin layer containing the aforementioned colorant and bio-based urethane (meth)acrylate. In other words, pattern layer 3 contains colorant and components derived from biomass.

[0696] Carbamate (meth)acrylates are obtained, for example, by reacting a polyol and an isocyanate with a hydroxyl ester of (meth)acrylate. In bio-carbamate (meth)acrylates, the polyol can be a plant-derived polyol, and the isocyanate can be a plant-derived isocyanate, or both the polyol and the isocyanate can be plant-derived substances.

[0697] As polyols, the following can be used: polyester polyols, which are the reaction products of polyfunctional alcohols and polyfunctional carboxylic acids; polyether polyols, which are the reaction products of polyfunctional alcohols and polyfunctional isocyanates; or polycarbonate polyols, which are the reaction products of polyfunctional alcohols and carbonates. The following describes each polyol.

[0698] <Polyester Polyols>

[0699] When a polyester polyol contains components derived from biomass, at least one of the polyfunctional alcohols and polyfunctional carboxylic acids contains components derived from biomass. Examples of polyester polyols containing components derived from biomass include the following.

[0700] • Reaction products of polyfunctional alcohols and polyfunctional carboxylic acids derived from biomass

[0701] • Reaction products of polyfunctional alcohols from fossil fuels and polyfunctional carboxylic acids from biomass

[0702] • Reaction products of polyfunctional alcohols from biomass and polyfunctional carboxylic acids from fossil fuels

[0703] Aliphatic polyfunctional alcohols derived from biomass can be used from plant sources such as corn, sugarcane, cassava, and sago palm. Examples of aliphatic polyfunctional alcohols derived from biomass include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), and hexamethylene glycol, all obtained from plant sources through the methods described below. These can be used alone or in combination.

[0704] Polypropylene glycol derived from biomass is produced by fermentation, which breaks down plant materials to obtain glucose, and by using glycerol via 3-hydroxypropionaldehyde (HPA). Compared to polypropylene glycol produced by the EO manufacturing method, polypropylene glycol produced by this bio-based fermentation method is preferred because it yields useful byproducts such as lactic acid from a safety perspective and also keeps manufacturing costs lower.

[0705] Butanediol derived from biomass can be produced by manufacturing diols from plant materials, fermenting them to obtain succinic acid, and then hydrogenating it.

[0706] Ethylene glycol derived from biomass can be produced, for example, from bioethanol obtained by conventional methods via ethylene.

[0707] As a polyfunctional alcohol derived from fossil fuels, compounds having two or more hydroxyl groups, preferably two to eight, per molecule can be used. Specifically, there are no particular limitations on the polyfunctional alcohol derived from fossil fuels; conventionally known substances can be used, such as, in addition to polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butanediol (BG), and hexamethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, trimethylolpropane, glycerol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, etc. These can be used alone or in combination of two or more.

[0708] As biomass-derived polyfunctional carboxylic acids, aliphatic polyfunctional carboxylic acids can be obtained from plant-based raw materials such as reproducible soybean oil, linseed oil, tung oil, coconut oil, palm oil, castor oil, etc., as well as recycled oils obtained from the recycling of waste edible oils mainly composed of these. Examples of biomass-derived aliphatic polyfunctional carboxylic acids include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acids. For example, sebacic acid is generated by the acid-base thermal decomposition of castor oil obtained from castor oil, with heptanol as a byproduct. In this invention, succinic acid or sebacic acid derived from biomass is particularly preferred. These can be used alone or in combination of two or more.

[0709] As polyfunctional carboxylic acids derived from fossil fuels, aliphatic or aromatic polyfunctional carboxylic acids can be used. For aliphatic polyfunctional carboxylic acids derived from fossil fuels, there are no particular limitations; conventionally known substances can be used, such as adipic acid, dodecanoic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acids, and their ester compounds. Similarly, for aromatic polyfunctional carboxylic acids derived from fossil fuels, there are no particular limitations; conventionally known substances can be used, such as isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, and their ester compounds. These can be used alone or in combination of two or more.

[0710] <Polyether polyols>

[0711] When a polyether polyol contains a component derived from biomass, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains a component derived from biomass. Examples of polyether polyols containing a component derived from biomass include the following.

[0712] • Reaction products of biomass-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates

[0713] • Reaction products of polyfunctional alcohols from fossil fuels and polyfunctional isocyanates from biomass

[0714] • Reaction products of polyfunctional alcohols from biomass and polyfunctional isocyanates from fossil fuels

[0715] As polyfunctional alcohols derived from biomass and polyfunctional alcohols derived from fossil fuels, the polyfunctional alcohols derived from biomass and polyfunctional alcohols derived from fossil fuels described above in the section on polyester polyols can be used.

[0716] As a polyfunctional isocyanate derived from biomass, it can be obtained by amidation and reduction of a dicarboxylic acid from a plant to a terminal amino group, followed by reaction with phosgene to convert the amino group into an isocyanate group. Examples of biomass-derived polyfunctional isocyanates include biomass-derived diisocyanates. Examples of biomass-derived diisocyanates include dimer diisocyanate (DDI), octamethylene diisocyanate, and decamethylene diisocyanate. Alternatively, plant-derived diisocyanates can be obtained by using amino acids from plants as raw materials and converting the amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by esterifying the carboxyl methyl group of lysine to convert the amino group into an isocyanate group. Furthermore, 1,5-pentamethylene diisocyanate is obtained by decarboxylating the carboxyl group of lysine to convert the amino group into an isocyanate group.

[0717] Other methods for synthesizing 1,5-pentamethylene diisocyanate include phosgenation and carbamate esterification. More specifically, phosgenation involves reacting 1,5-pentamethylenediamine or its salt directly with phosgene, or suspending pentamethylenediamine hydrochloride in an inert solvent and reacting it with phosgene to synthesize 1,5-pentamethylenediisocyanate. Carbamate esterification involves first carbamateing 1,5-pentamethylenediamine or its salt to generate pentamethylenedicarbamate (PDC), and then synthesizing 1,5-pentamethylenediisocyanate through thermal decomposition. In this invention, a preferred polyisocyanate is the 1,5-pentamethylenediisocyanate-based polyisocyanate manufactured by Mitsui Chemicals Co., Ltd. (trade name: STABiO (registered trademark)).

[0718] As a polyfunctional isocyanate derived from fossil fuels, there are no particular limitations, and conventionally known substances can be used, such as: toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylenebis(phenylene isocyanate) (MDI), dextrin diisocyanate, benzyl diisocyanate, phenyl dimethyl diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-dibenzyl diisocyanate, and other aromatic diisocyanates. In addition, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate can be listed; alicyclic diisocyanates such as 1,4-cyclohexylene diisocyanate, 4,4-methylenebis(cyclohexyl)isocyanate, 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI can also be listed. These can be used alone or in combination of two or more.

[0719] <Polycarbonate polyols>

[0720] When polycarbonate polyols contain components derived from biomass, the reaction product of a polyfunctional alcohol containing components derived from biomass and a carbonate derived from fossil fuels can be used as the polycarbonate polyol. Alternatively, the reaction product of a polyfunctional alcohol containing components derived from fossil fuels and a carbonate derived from biomass can be used. Examples of carbonates include dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, and diphenyl carbonate. They can be used alone or in combination of two or more.

[0721] As a biomass-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol described in the above-mentioned polyester polyols can be used.

[0722] <Isocyanate compounds>

[0723] Next, the isocyanate compound will be described. As an isocyanate compound containing components derived from biomass, a biomass-derived polyfunctional isocyanate as described in the section on polyether polyols can be used.

[0724] Hydroxyl (meth)acrylate

[0725] Next, hydroxy methacrylates will be described. Examples of hydroxy methacrylates include: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and 2-hydroxy-3-phenoxypropyl methacrylate, which have one methacryloyl group; and hydroxy methacrylates with two or more methacryloyl groups, such as di(meth)acrylate, pentaerythritol tri(meth)acrylate, di(trimethylolpropane)tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and sorbitol penta(meth)acrylate. These can be used individually or in combination of two or more.

[0726] In addition to the aforementioned bio-carbamate (meth)acrylate, the adhesive resin of pattern layer 3 may also contain nitrocellulose. That is, pattern layer 3 may contain the aforementioned bio-carbamate (meth)acrylate, or it may contain nitrocellulose in addition to bio-carbamate (meth)acrylate.

[0727] Nitrocellulose

[0728] Nitrocellulose is a nitro-substituted cellulose resin formed by nitrifying a portion of the hydroxyl groups in the cellulose backbone. The cellulose backbone of nitrocellulose resin is a biomass material. As nitrocellulose, ordinary nitrocellulose can be used without hindrance, but nitrocellulose formed by replacing each glucose unit constituting the cellulose backbone with an average of 1.3 to 2.7 nitro groups is particularly preferred.

[0729] Nitrocellulose exists in L-form and H-form based on its molecular weight. Considering its solubility in organic solvents, the L-form is preferred.

[0730] The patterned layer 3 preferably has a biomass content of 5% or more, more preferably 5% or more and 50% or less, and even more preferably 10% or more and 50% or less. If the biomass content is within the above range, the amount of fossil fuel used can be reduced, thereby reducing the environmental impact. The dried weight of the patterned layer 3 is preferably 0.1 g / m³. 2 ]Above 15 [g / m 2 The following, or more preferably, is 3 g / m 2 ]Above 10 [g / m 2 The following, and more preferably 6 g / m 2 Above 9 [g / m 2 The pattern layer 3 preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 0.5 μm or more and 5 μm or less, and even more preferably 0.7 μm or more and 3 μm or less. It should be noted that multiple pattern layers 3 having such weight or thickness may also be provided.

[0731] Regarding "biomass content", for example in the case of biocarbamate (meth)acrylate, as described above, it is determined as a value for the carbon content from biomass measured using radiocarbon (C14) determination.

[0732] Furthermore, regarding "biomass content," for example, in the case of nitrocellulose, since each glucose unit (formula = 172) constituting the cellulose backbone as the starting material contains 3 hydroxyl groups, 1 to 3 of these hydroxyl groups can undergo nitration (hydrogen is replaced by nitro groups (non-biomass material, formula = 46)). Thus, assuming the original cellulose backbone is composed of 100% by weight of biomass material, and with an average of n nitro groups being replaced per glucose unit, the proportion (by weight) of biomass material in the total nitrocellulose molecule can be calculated using (172-n) × 100 / (172-n + 46n).

[0733] Regarding the proportion of biomass material in the overall nitrocellulose molecule, it is approximately 78.8% by weight when each glucose unit constituting the cellulose backbone is replaced by an average of one nitro group, approximately 64.9% by weight when replaced by two nitro groups, and approximately 55.0% by weight when replaced by three nitro groups (calculated values ​​in the above formula).

[0734] Furthermore, when the thickness of the pattern layer 3 is less than 10 μm, the printability of the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.

[0735] In addition, to impart various functions, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesives, desiccants, curing agents, curing accelerators, and curing delayers can be added to pattern layer 3.

[0736] The pattern for pattern layer 3 can be any pattern, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, text, symbols, single-color pigments, or combinations thereof. Additionally, to improve the concealment of decorative piece 1, a concealing layer can be provided between pattern layer 3 and colored substrate layer 2. This concealing layer can be formed, for example, using opaque printing inks or coatings containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0737] Alternatively, the pattern layer 3 may be configured to have a solid-coated colored substrate layer to conceal the color / pattern of the base of the decorative piece 1, and a pattern layer for attaching a design-specific pattern.

[0738] <Adhesive Layer>

[0739] Adhesive layer 4 is stacked on one side of pattern layer 3 (in) Figure 1 On the top side (the middle side), there is a layer used to bond the pattern layer 3 and the transparent resin layer 5.

[0740] Materials used for adhesive layer 4 include, for example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, and polyolefin-based resins. In particular, considering adhesion to the transparent resin layer 5, polyolefin-based resins are preferred.

[0741] <Transparent resin layer>

[0742] The transparent resin layer 5 is stacked on one side of the adhesive layer 4 (in Figure 1 On the upper side (the middle side), there is a transparent resin layer formed of a resin composition containing the aforementioned polyethylene derived from biomass (from plants). More specifically, the transparent resin layer 5 is a resin layer formed of a resin composition containing polyethylene derived from biomass, which is polymerized from monomers containing ethylene derived from biomass. That is, in the transparent resin layer 5, a resin composition containing polyethylene derived from biomass used in the colored substrate layer 2 may also be used. In addition, it may contain polyethylene derived from fossil fuels, which is polymerized from monomers containing at least one of ethylene derived from fossil fuels and α-olefins, and ethylene derived from fossil fuels.

[0743] The transparent resin layer 5 may contain ethylene derived from biomass at a concentration of 5% or more by mass relative to the total amount of the transparent resin layer 5, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass. If the concentration of ethylene derived from biomass in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the past, and a carbon-neutral decorative sheet can be achieved.

[0744] The density of the transparent resin layer 5 is 0.92 g / cm³. 3 Above 0.99 g / cm³ 3 Within the range below, preferably 0.94 g / cm³ 3 Above 0.98 g / cm³ 3 Within the range below, more preferably 0.95 g / cm³ 3 Above 0.97 g / cm³ 3 The density is within the range below. The density of the transparent resin layer 5 is determined by method A specified in JIS K7112-1980 after annealing as described in JIS K6760-1995. If the density of the transparent resin layer 5 is 0.92 g / cm³... 3 The above can improve the rigidity of the transparent resin layer 5. Additionally, if the density of the transparent resin layer 5 is 0.99 g / cm³, the rigidity can be increased. 3 The following steps can improve the transparency and mechanical strength of the transparent resin layer 5.

[0745] The transparent resin layer 5 has a thickness of 55-150 μm, preferably 55-100 μm, and more preferably 60-80 μm.

[0746] The transparent resin layer 5 may contain high-density polyethylene derived from biomass as the biomass-derived polyethylene.

[0747] In addition, the transparent resin layer 5 may contain polyethylene derived from biomass, which is a blend of high-density polyethylene from biomass and low-density polyethylene from biomass in the range of 100:0 to 20:80.

[0748] In addition, the overall biomass content of the transparent resin layer 5 can be in the range of 10% to 90%.

[0749] The manufacturing method of the transparent resin layer 5 is not particularly limited and can be manufactured by conventionally known methods. In the seventh embodiment, it is preferably formed by extrusion molding, and more preferably by T-die molding or blow molding.

[0750] In the seventh embodiment, the transparent resin layer 5 and the colored substrate layer 2 preferably satisfy the following specific relationships regarding density, thickness, and biomass density (ethylene concentration from biomass).

[0751] In the seventh embodiment, the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 preferably satisfy d2>d1. This is because formability is required for the transparent resin layer 5 to function, and productivity is required for the colored substrate layer 2 to function.

[0752] It should be noted that the ratio (d2 / d1) of the density d1 of the transparent resin layer 5 to the density d2 of the colored substrate layer 2 is preferably in the range of 1.1 to 1.5, more preferably in the range of 1.1 to 1.3, and even more preferably in the range of 1.1 to 1.2. By ensuring that the density ratio of the transparent resin layer to the colored substrate layer is within this range, even when using polyethylene derived from biomass, it can possess the extrusion suitability and bending processing suitability required for decorative sheets.

[0753] In the seventh embodiment, the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored substrate layer 2 preferably satisfy t1 ≥ t2. This is because a thickness is required for the transparent resin layer 5 to function, but a thickness similar to that of the transparent resin layer 5 is not required for the colored substrate layer 2 to function.

[0754] It should be noted that the ratio (t1 / t2) of the thickness t1 of the transparent resin layer 5 to the thickness t2 of the colored substrate layer 2 is preferably in the range of 1.1 to 3, more preferably in the range of 1.1 to 2, and even more preferably in the range of 1.1 to 1.5.

[0755] In the seventh embodiment, the ethylene concentration C1 from biomass in the transparent resin layer 5 and the ethylene concentration C2 from biomass in the colored substrate layer 2 preferably satisfy C1 > C2. This is because, since the transparent resin layer 5 is thick and uses a large amount of ethylene in order to function as a transparent resin layer 5, the amount of fossil fuel used can be further reduced by increasing the biomass content of the transparent resin layer 5.

[0756] Nucleating agents (e.g., "Rikemaster CN-002" manufactured by RichenVitamin Co., Ltd.) may also be added to the biomass-derived polyethylene that forms the transparent resin layer 5.

[0757] Based on the mass of polyethylene, the nucleating agent is preferably added to polyethylene in the range of 500 to 2000 ppm, and more preferably in the range of 1500 to 2000 ppm.

[0758] As needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers can be added to the transparent resin layer 5.

[0759] It should be noted that the transparent resin layer 5 preferably has a degree of transparency (colorless transparent, colored transparent, semi-transparent) that allows the pattern of the pattern layer 3 to be seen through the surface (top) of the decorative sheet 1.

[0760] It should be noted that in the seventh embodiment, polyethylene derived from biomass was described as the biomass-derived resin constituting the transparent resin layer 5, but the present invention is not limited thereto. For example, polypropylene or polybutene derived from biomass may be used instead of the aforementioned biomass-derived polyethylene. That is, in the seventh embodiment, polyolefins derived from biomass can be widely used as the biomass-derived resin constituting the transparent resin layer 5.

[0761] <Surface Protective Layer>

[0762] Surface protective layer 6 is stacked on one side of transparent resin layer 5 (in) Figure 1 The middle (upper side) is a layer designed to give decorative piece 1 functions such as weather resistance, damage resistance, stain resistance, and design.

[0763] Alternatively, the surface protective layer 6 can be formed using a thermosetting resin, an ionizing radiation-cured resin, or, for example, an acrylic resin composition.

[0764] In addition, depending on the requirements, the surface protective layer 6 may contain various additives such as weather resistant agents, plasticizers, stabilizers, fillers, dispersants, dyes, pigments and other colorants, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst trapping agents, colorants, light scattering agents, and gloss modifiers. Furthermore, depending on the requirements, the surface protective layer 6 may also contain functional additives such as antibacterial agents and antifungal agents.

[0765] <Concave and convex parts>

[0766] The uneven portion 7 is formed by recesses provided at multiple locations in the transparent resin layer 5 and the surface protective layer 6.

[0767] <Primer layer>

[0768] The primer layer 8 is a base layer used to improve the adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9.

[0769] In addition, the primer layer 8 is laminated on the other side of the colored substrate layer 2 (in Figure 1(The middle is the lower side surface).

[0770] In addition, the primer layer 8 is formed, for example, using polyester resin, organic additives, pigments, etc.

[0771] It should be noted that, in order to improve corrosion resistance, anti-rust pigments can be added to the primer layer 8.

[0772] The thickness of the primer layer 8 is, for example, in the range of 1 [μm] to 10 [μm].

[0773] It should be noted that the above-described embodiments are an example of the present invention. The present invention is not limited to the above-described embodiments. Even in ways other than those described, as long as they do not depart from the technical concept of the present invention, various changes can be made according to the design, etc.

[0774] (Effects of the 7th embodiment)

[0775] If it is the decorative piece 1 of the seventh embodiment, it can achieve the effects described below.

[0776] (1) The colored substrate layer 2 and the transparent resin layer 5 are resin layers formed from a resin composition containing a biomass-derived polyolefin polymerized from monomers comprising olefins derived from biomass. The transparent resin layer 5 contains 5% by mass or more of the olefin derived from biomass and has a content of 0.92 g / cm³. 3 Above 0.99 g / cm³ 3 Within the following density range, the colored substrate layer 2 contains more than 5% by mass of olefins derived from biomass and has a density of 0.92 g / cm³. 3 The above is 1.12 g / cm³ 3 Within the following density range, pattern layer 3 contains colorants and components derived from biomass.

[0777] Therefore, it is possible to provide decorative sheets that can reduce the use of fossil fuels by using materials derived from plants, while maintaining physical properties suitable for use as decorative sheets.

[0778] (2) Pattern layer 3 is a resin layer containing a resin composition comprising at least a polyol, an isocyanate compound and a (meth)acrylate hydroxy ester, namely a urethane (meth)acrylate, wherein at least one of the polyol, isocyanate compound and (meth)acrylate hydroxy ester contained in the resin composition contains a component derived from biomass.

[0779] Therefore, it is possible to provide decorative sheets that can reliably reduce the use of fossil fuels by using materials derived from plants, and reliably maintain physical properties suitable for use as decorative sheets.

[0780] (3) The polyol that constitutes the bio-urethane (meth) acrylate contained in the pattern layer 3 is a polyester polyol containing bio-derived components, a polyether polyol containing bio-derived components, or a polycarbonate polyol containing bio-derived components.

[0781] Therefore, it is possible to provide decorative sheets that can more reliably reduce the use of fossil fuels by using materials derived from plants, and can more reliably maintain the physical properties suitable for use as decorative sheets.

[0782] (4) The polyester polyols that are constituent elements of the above-mentioned bio-carbamate (meth)acrylates are either polyfunctional alcohols containing components from biomass and polyfunctional carboxylic acids containing components from fossil fuels, or polyfunctional alcohols containing components from fossil fuels and polyfunctional carboxylic acids containing components from biomass.

[0783] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0784] (5) The polyether polyols that are constituent elements of the above-mentioned bio-carbamate (meth)acrylates are reaction products of polyfunctional alcohols containing components from biomass and polyfunctional isocyanates containing components from fossil fuels, or reaction products of polyfunctional alcohols containing components from fossil fuels and polyfunctional isocyanates containing components from biomass.

[0785] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0786] (6) The polycarbonate polyols that are constituent elements of the above-mentioned bio-carbamate (meth)acrylates are either the reaction products of polyfunctional alcohols containing components from biomass and carbonates containing components from fossil fuels, or the reaction products of polyfunctional alcohols containing components from fossil fuels and carbonates containing components from biomass.

[0787] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0788] (7) The isocyanate compound that is a component of the bio-carbamate (meth)acrylate contained in the pattern layer 3 is an isocyanate compound containing components derived from biomass.

[0789] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0790] (8) A decorative sheet 1 having a substrate 9 and a decorative sheet 1 laminated on at least one side of the substrate 9.

[0791] Therefore, it is possible to provide decorative materials that can reduce the use of fossil fuels by using materials derived from plants, while maintaining physical properties suitable for use as decorative panels.

[0792] Example 5

[0793] Hereinafter, the decorative materials of Examples 1 to 9 and the decorative materials of Examples 1 to 3 will be described with reference to the 7th embodiment.

[0794] (Example 1)

[0795] After applying corona discharge treatment to one side of the substrate, a pattern layer, a urethane adhesive layer, a maleic anhydride modified polyethylene resin layer (transparent adhesive layer), a transparent resin layer, and a surface protective layer mainly composed of an acrylic resin composition are sequentially laminated on that side of the substrate. Furthermore, after applying corona discharge treatment to the other side of the substrate, a primer layer (thickness: 1-2 μm) composed of polyester urethane resin is formed. Thus, the decorative sheet of Example 1 (total thickness: 135 μm) is obtained.

[0796] In Example 1, a colored substrate layer (thickness: 55 μm) was used as the substrate, formed from a resin composition containing high-density polyethylene from biomass and low-density polyethylene from fossil fuels. The colored substrate layer was obtained by calendering this resin composition. The biomass content of the thus formed colored substrate layer was 80%, and the density of the colored substrate layer was 1.08 g / cm³. 3 ].

[0797] For the transparent resin layer, a transparent resin layer (thickness: 80 μm) is formed using a resin composition containing biomass-derived polyethylene (Braskem Corporation's "Biomass Polyethylene"). This biomass-derived polyethylene is a resin obtained by blending high-density polyethylene (SHC7260) and low-density polyethylene (SPB681) derived from biomass at a ratio (high-density polyethylene / low-density polyethylene) of 80 / 20. The transparent resin layer is obtained by extrusion lamination of this resin. The resulting transparent resin layer has a biomass content of 94% and a density of 0.95 g / cm³. 3 ].

[0798] The adhesive resin for the patterned layer uses a bio-urethane (meth)acrylate, a reaction product of a polyester polyol containing components derived from biomass, an isocyanate compound from fossil fuels, and a (meth)acrylate hydroxyl ester from fossil fuels. The polyester polyol containing components derived from biomass is a reaction product of a polyfunctional alcohol containing components derived from biomass and a polyfunctional carboxylic acid from fossil fuels.

[0799] (Example 2)

[0800] The decorative sheet of Example 2 was obtained in the same manner as in Example 1, except that the polyester polyol in the bio-urethane (meth) acrylate, which is the adhesive resin of the pattern layer, was used as the reaction product of a polyfunctional alcohol from fossil fuels and a polyfunctional carboxylic acid containing components from biomass.

[0801] (Example 3)

[0802] The adhesive resin used as the pattern layer is bio-urethane (meth)acrylate. The reaction product of the bio-urethane (meth)acrylate, which is a polyester polyol derived from fossil fuels, an isocyanate compound containing components derived from biomass, and a (meth)acrylate hydroxyl ester derived from fossil fuels, was used. Otherwise, the decorative sheet of Example 3 was obtained in the same manner as in Example 1.

[0803] (Example 4)

[0804] The adhesive resin for the pattern layer is a polyol in bio-urethane (meth)acrylate, and a polyether polyol is used. Otherwise, the decorative sheet of Example 4 is obtained in the same manner as in Example 1. Specifically, the polyether polyol is a reaction product of a polyfunctional alcohol containing components from biomass and a polyfunctional isocyanate from fossil fuels.

[0805] (Example 5)

[0806] The decorative sheet of Example 5 was obtained in the same manner as in Example 4, except that the adhesive resin of the pattern layer was a polyether polyol in bio-urethane (meth) acrylate, which was a reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional isocyanate containing components derived from biomass.

[0807] (Example 6)

[0808] The adhesive resin used as the pattern layer is a polyol in bio-urethane (meth) acrylate, and a polyether polyol derived from fossil fuels is used. Otherwise, the decorative sheet of Example 6 is obtained in the same manner as in Example 3.

[0809] (Example 7)

[0810] The adhesive resin for the pattern layer is a polyol in bio-urethane (meth)acrylate, and a polycarbonate polyol is used. Otherwise, the decorative sheet of Example 7 is obtained in the same manner as in Example 1. Specifically, the polycarbonate polyol is a reaction product of a polyfunctional alcohol containing components from biomass and a carbonate from fossil fuels.

[0811] (Example 8)

[0812] The adhesive resin used as the pattern layer is a polyol in bio-urethane (meth) acrylate, and a polycarbonate polyol derived from fossil fuels is used. Otherwise, the decorative sheet of Example 8 is obtained in the same manner as in Example 3.

[0813] (Example 9)

[0814] High-density polyethylene (SHC7260) from biomass and low-density polyethylene (SPB681) from biomass were blended in a ratio (high-density polyethylene / low-density polyethylene) of 100 / 0. A transparent resin layer was obtained by extruding and laminating the resin. Otherwise, the decorative sheet of Example 9 was obtained in the same manner as in Example 1.

[0815] (See Example 1 for reference)

[0816] Except that the pattern layer was formed by urethane-based printing ink, the decorative sheet of Reference Example 1 was obtained in the same manner as in Example 1.

[0817] (See Example 2 for reference)

[0818] Except that a transparent resin layer was obtained by extruding and laminating homopolymer polypropylene resin derived from fossil fuels produced by Prime Polymer Co., Ltd., the decorative sheet of Reference Example 2 was obtained in the same manner as in Example 1.

[0819] (See Example 3 for reference)

[0820] Except that the colored substrate layer was obtained using only colored polyethylene resin derived from fossil fuels, the decorative sheet of Reference Example 3 was obtained in the same manner as in Example 1.

[0821] (Performance evaluation, evaluation results)

[0822] For the decorative sheets of Examples 1 to 9 and the decorative sheets of Reference Examples 1 to 3, the following were evaluated: “haze of transparent resin layer (%)”, “pencil hardness”, “Hoffman scratch test”, “extrusion suitability”, and “bending whitening”. The following methods were used as the evaluation methods.

[0823] <Haze of the transparent resin layer (%)>

[0824] Using an ultraviolet-visible-near infrared spectrophotometer (manufacturer: Shimadzu Corporation, model: UV-3600), the haze (%) of the transparent resin layer was measured.

[0825] Resin having the same composition as the transparent resin layer of each example / reference example was extruded within the range of a thickness of 70 [μm] or more and 80 [μm] or less to obtain a resin film. The haze at a wavelength of 555 nm was measured using a spectrophotometer (integrating sphere), and the haze was evaluated. Then, a case where the haze was less than 15% was evaluated as "◎", a case where the haze was 15% or more and less than 25% was evaluated as "○", and a case where the haze was 25% or more was evaluated as "×".

[0826] It should be noted that in this example, "◎" and "○" were regarded as qualified.

[0827] <Pencil hardness>

[0828] The pencil hardness was measured by a pencil hardness testing machine (automatic) (manufacturer: Yoshimitsu Seiki Co., Ltd., model: C221A).

[0829] After performing a pencil hardness test on the decorative material including the decorative sheet of each example / reference example using pencils with different hardnesses, the damage (depression) generated on the surface (surface protective layer) was confirmed, and the surface hardness was evaluated. Then, a case where damage occurred on the surface after performing a pencil hardness test using a pencil with a hardness of 2B or more was evaluated as "◎", and a case where damage occurred on the surface after performing a pencil hardness test using a pencil with a hardness of 4B or more was evaluated as "○". In addition, a case where damage occurred on the surface after performing a pencil hardness test using a pencil with a hardness of 5B or less was evaluated as "×".

[0830] It should be noted that in this example, "◎" and "○" were regarded as qualified.

[0831] <Hoffman scratch test>

[0832] The Hoffman scratch test was conducted as follows: A scratching blade (a cylindrical blade with a diameter of Φ7) was set to contact the surface of the decorative sheet at an angle of 45 degrees, and the testing machine was moved on the decorative sheet.

[0833] Scratches were generated by gradually increasing the load (heavy object) within the range of 200 to 2000 g (increments of 200 g each), and the load (g) at which damage occurred on the surface of the sample was evaluated. It should be noted that in the case where damage occurred at a load of 800 g, "600 g" was recorded as the tolerance load in the table. <...>

[0834] It should be noted that in this example, a case where the tolerance load was "200 g" was regarded as unqualified.

[0835] <Extrusion adaptability>

[0836] The transparent resin layer was extruded to confirm its production suitability (extrusion suitability).

[0837] As a result, if the product can be manufactured (formed) without any problems, it is marked as "0" (qualified). On the other hand, situations where defects may occur are marked as "△" (unqualified).

[0838] <Bending Whitening>

[0839] Use the decorative sheet (i.e., decorative material) pasted on the MDF to confirm the suitability of V-cut processing (whether there is bending whitening).

[0840] As a result, cases without whitening were marked as "○" (pass), cases with slight whitening were marked as "△" (pass), and cases with whitening were marked as "×" (fail).

[0841]

[0842]

[0843] The results of evaluating various properties using the above methods show that the decorative sheets of Examples 1 to 9 exhibited superior performance, equivalent to or better than that of Reference Examples 1-3, in all evaluation tests. That is, it can be seen that the decorative sheets of Examples 1 to 9, by using materials derived from plants, can reduce the use of fossil fuels and maintain physical properties suitable for use as decorative sheets.

[0844] (Eighth embodiment)

[0845] The following is for reference Figure 1 The composition of decorative material 10 is explained.

[0846] like Figure 1 As shown, the decorative material 10 comprises a decorative piece 1 and a substrate 9. It should be noted that the specific composition of the decorative piece 1 will be described later.

[0847] It should be noted that the composition of the decorative material 10 in the eighth embodiment is the same as that in the first embodiment, except for the composition of the decorative piece 1. Therefore, the description of the composition other than the decorative piece 1 is omitted.

[0848] (Composition of decorative pieces)

[0849] like Figure 1 As shown, the decorative piece 1 has a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface protective layer 6, a raised and recessed portion 7, and a primer layer 8.

[0850] <Colored substrate layer>

[0851] The colored substrate layer 2 is a resin layer formed using thermoplastic resin, which is a colored resin layer formed from a resin composition containing polyethylene derived from biomass (from plants).

[0852] The composition of the colored substrate layer 2 will be described in detail below.

[0853] (Polyethylene derived from biomass)

[0854] In the eighth embodiment, the polyethylene derived from biomass is polymerized from monomers containing ethylene derived from biomass. There is no particular limitation on the ethylene derived from biomass; ethylene produced by conventionally known methods can be used. Since ethylene derived from biomass is used as the monomer source, the polymerized polyethylene is derived from biomass.

[0855] It should be noted that the raw material monomers of polyethylene may not contain 100% by mass ethylene derived from biomass.

[0856] The monomers used as raw materials for polyethylene derived from biomass may further contain at least one of ethylene derived from fossil fuels and α-olefins derived from fossil fuels, or may further contain α-olefins derived from biomass.

[0857] There is no particular limitation on the number of carbon atoms in the aforementioned α-olefins; α-olefins with 3 to 20 carbon atoms are generally used, with butene, hexene, or octene being preferred. This is because butene, hexene, or octene can be manufactured by polymerizing ethylene, which is a feedstock derived from biomass. Furthermore, by containing such α-olefins, the polymerized polyethylene has an alkyl group as a branched structure, thus making it more flexible than simple linear polyethylene.

[0858] By using ethylene as a feedstock from biomass, it is theoretically possible to produce it from 100% biomass components.

[0859] The ethylene concentration derived from biomass in the aforementioned polyethylene (hereinafter sometimes referred to as "biomass content") is a value obtained by measuring the carbon content derived from biomass using radiocarbon (C14) determination. It is known that atmospheric carbon dioxide contains a certain proportion (105.5 pMC) of C14; therefore, the C14 content in plants that absorb atmospheric carbon dioxide (e.g., corn) is also approximately 105.5 pMC. Furthermore, it is known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in polyethylene, the proportion of carbon derived from biomass can be calculated. In the seventh embodiment, the C14 content in polyethylene is set as P. C14 Carbon content from biomass at that time Pbio It can be calculated as follows.

[0860] P bio (%)=P C14 / 105.5×100

[0861] In the eighth embodiment, theoretically, if all ethylene from biomass is used as the raw material for polyethylene, the concentration of ethylene from biomass is 100%, and the biomass degree of the polyethylene from biomass is 100. Furthermore, in fossil fuel polyethylene manufactured solely from fossil fuel raw materials, the concentration of ethylene from biomass is 0%, and the biomass degree of the polyethylene from fossil fuels is 0.

[0862] In the eighth embodiment, the polyethylene derived from biomass or the decorative sheet containing such polyethylene does not require a biomass content of 100.

[0863] In embodiment 8, the polymerization method for monomers containing ethylene derived from biomass is not particularly limited, and can be carried out using conventionally known methods. The polymerization temperature and polymerization pressure can be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and conventionally known apparatus can be used. Hereinafter, an example of a polymerization method for monomers containing ethylene will be described.

[0864] The polymerization method for ethylene polymers or copolymers of ethylene and α-olefins can be appropriately selected based on the type of target polyethylene, such as the density or branching of high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). For example, it is preferable to use multi-site catalysts such as Ziegler-Natta catalysts or single-site catalysts such as metallocene catalysts as polymerization catalysts, and to carry out the polymerization in one or more stages using any of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[0865] In addition, polyethylene derived from biomass can be a polymer of ethylene alone or a copolymer of ethylene and α-olefins, or a mixture of two or more.

[0866] (A resin composition containing polyethylene derived from biomass)

[0867] In the eighth embodiment, the resin composition contains the aforementioned polyethylene as a main component. The resin composition contains at least 5% by mass, preferably 5 to 95% by mass, and more preferably 25 to 75% by mass of ethylene derived from biomass relative to the total resin composition. If the concentration of ethylene derived from biomass in the resin composition is 5% by mass or more, the amount of fossil fuel used can be reduced compared to conventional methods, enabling the achievement of carbon-neutral decorative sheets.

[0868] The above-mentioned resin composition may contain two or more types of polyethylene with different biomass concentrations, as long as the concentration of ethylene from biomass as a whole is within the above-mentioned range.

[0869] The resin composition described above may further comprise polyethylene derived from fossil fuels, which is obtained by polymerizing a monomer comprising at least one of ethylene and α-olefins derived from fossil fuels, and ethylene derived from fossil fuels. That is, in embodiment 8, the resin composition may also be a mixture of polyethylene derived from biomass and polyethylene derived from fossil fuels. The mixing method is not particularly limited, and conventionally known methods can be used. For example, dry blending or melt blending may be employed.

[0870] According to the eighth embodiment, the resin composition contains preferably 5 to 90% by mass, more preferably 25 to 75% by mass, of polyethylene derived from biomass; and preferably 10 to 95% by mass, more preferably 25 to 75% by mass, of polyethylene derived from fossil fuels. Even when using a resin composition with such a mixture, as long as the concentration of ethylene derived from biomass as a whole is within the above-mentioned range, it is acceptable.

[0871] In the resin composition manufactured in the above-described resin composition manufacturing process, various additives may be added in addition to polyethylene as the main component, without impairing its properties. Examples of additives include plasticizers, UV stabilizers, anti-staining agents, matting agents, deodorizers, flame retardants, weathering agents, antistatic agents, yarn friction reducers, slip agents, anti-sticking agents, antioxidants, ion exchangers, and coloring pigments. These additives are preferably added in the range of 1 to 20% by mass, more preferably 1 to 10% by mass, relative to the total resin composition.

[0872] As described above, the coloring substrate layer 2 contains ethylene derived from biomass at a concentration of 5% or more by mass relative to the total amount of the coloring substrate layer 2, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass. If the concentration of ethylene derived from biomass in the coloring substrate layer 2 is 5% or more by mass, the amount of fossil fuel used can be reduced compared to the past, and a carbon-neutral decorative sheet can be achieved.

[0873] The colored substrate layer 2 has a density of 0.92 g / cm³. 3 The above is 1.12 g / cm³ 3 Within the range below, preferably 0.98 g / cm³ 3 The above 1.10 [g / cm] 3The density is within the range below. The density of the colored substrate layer 2 is determined by method A specified in JIS K7112-1980 after annealing as described in JIS K6760-1995. If the density of the colored substrate layer 2 is 0.92 g / cm³, the density is determined by the following method. 3 The above can improve the rigidity of the colored substrate layer 2. Additionally, if the density of the colored substrate layer 2 is 1.12 g / cm³, the rigidity of the substrate layer 2 can be improved. 3 The following steps can improve the transparency and mechanical strength of the colored substrate layer 2.

[0874] In the colored substrate layer 2, the polyethylene derived from biomass can be any of the following: polyethylene containing both high-density polyethylene and low-density polyethylene derived from biomass; polyethylene containing both high-density polyethylene derived from biomass and low-density polyethylene derived from fossil fuels; or polyethylene containing low-density polyethylene derived from biomass within high-density polyethylene derived from fossil fuels. The overall biomass content of the colored substrate layer 2 can be in the range of 10% to 90%.

[0875] It should be noted that high-density polyethylene derived from biomass refers to polyethylene with a density exceeding 0.94. Conversely, low-density polyethylene derived from biomass refers to polyethylene with a density below 0.94.

[0876] In the colored substrate layer 2, the polyethylene derived from biomass can be a blend of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) (which can be derived from either biomass or fossil fuels) in a ratio ranging from 95:5 to 70:30. When the content of LDPE is low, the film-forming stability is poor; when the content of LDPE is high, the film becomes too soft.

[0877] The manufacturing method of the colored substrate layer 2 is not particularly limited and can be manufactured by conventionally known methods. In the eighth embodiment, it is preferably formed by calendering.

[0878] Additionally, as needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers may be added to the colored substrate layer 2.

[0879] The thickness of the colored substrate layer 2 is preferably in the range of 40 μm to 200 μm, more preferably 51 μm to 120 μm, and even more preferably 55 μm to 100 μm. This is because when the thickness of the colored substrate layer 2, which is made of polyethylene derived from biomass, is 40 μm or more, it can absorb unevenness and steps in the flooring material or the like used as the substrate, thereby allowing for a good installation of the decorative sheet 1. Furthermore, when the thickness of the colored substrate layer 2 is 200 μm or less, a colored substrate layer 2 exceeding the required thickness will not be formed, thereby reducing the manufacturing cost of the decorative sheet 1.

[0880] It should be noted that in the eighth embodiment, polyethylene derived from biomass was described as the resin constituting the coloring substrate layer 2, but the present invention is not limited thereto. For example, polypropylene or polybutene derived from biomass may be used instead of the aforementioned polyethylene derived from biomass. That is, in the eighth embodiment, polyolefins derived from biomass can be widely used as the resin constituting the coloring substrate layer 2.

[0881] <Pattern Layer>

[0882] Pattern layer 3 is stacked on one side of colored substrate layer 2 (in) Figure 1 The top surface (the middle one) is used to attach layers for adding patterns to give the design.

[0883] In addition, the pattern layer 3 is formed using printing inks or coatings. The printing inks or coatings that form the pattern layer 3 are formed, for example, by dissolving or dispersing colorants such as dyes or pigments together with a suitable binder resin in a suitable diluent.

[0884] The printing inks or coatings that form the pattern layer 3 are applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roller coating.

[0885] The pattern layer 3 is formed by containing the aforementioned colorant and binder resin. Hereinafter, the binder resin used for the pattern layer 3 in the eighth embodiment will be described.

[0886] [Adhesive Resin]

[0887] The adhesive resin contained in pattern layer 3 comprises a resin composition containing at least a polyol, an isocyanate compound, and a (meth)acrylate hydroxyl ester, namely, urethane (meth)acrylate. Furthermore, in pattern layer 3, at least one of the polyol, isocyanate compound, or (meth)acrylate hydroxyl ester constituting the aforementioned urethane (meth)acrylate contains a component derived from biomass. At least any one of the polyol, isocyanate compound, or (meth)acrylate hydroxyl ester may or may not contain a component derived from biomass. In the following description, urethane (meth)acrylate containing a component derived from biomass is also referred to as bio-urethane (meth)acrylate.

[0888] That is, pattern layer 3 is a resin layer containing the aforementioned colorant and bio-based urethane (meth)acrylate. In other words, pattern layer 3 contains colorant and components derived from biomass.

[0889] Carbamate (meth)acrylates are obtained, for example, by reacting a polyol and an isocyanate with a hydroxyl ester of (meth)acrylate. In bio-carbamate (meth)acrylates, the polyol can be a plant-derived polyol, and the isocyanate can be a plant-derived isocyanate, or both the polyol and the isocyanate can be plant-derived substances.

[0890] As polyols, the following can be used: polyester polyols, which are the reaction products of polyfunctional alcohols and polyfunctional carboxylic acids; polyether polyols, which are the reaction products of polyfunctional alcohols and polyfunctional isocyanates; or polycarbonate polyols, which are the reaction products of polyfunctional alcohols and carbonates. The following describes each polyol.

[0891] <Polyester Polyols>

[0892] When a polyester polyol contains components derived from biomass, at least one of the polyfunctional alcohols and polyfunctional carboxylic acids contains components derived from biomass. Examples of polyester polyols containing components derived from biomass include the following.

[0893] • Reaction products of polyfunctional alcohols and polyfunctional carboxylic acids derived from biomass

[0894] • Reaction products of polyfunctional alcohols from fossil fuels and polyfunctional carboxylic acids from biomass

[0895] • Reaction products of polyfunctional alcohols from biomass and polyfunctional carboxylic acids from fossil fuels

[0896] Aliphatic polyfunctional alcohols derived from biomass can be used from plant sources such as corn, sugarcane, cassava, and sago palm. Examples of aliphatic polyfunctional alcohols derived from biomass include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene glycol (BG), and hexamethylene glycol, all obtained from plant sources through the methods described below. These can be used alone or in combination.

[0897] Polypropylene glycol derived from biomass is produced by fermentation, which breaks down plant materials to obtain glucose, and by using glycerol via 3-hydroxypropionaldehyde (HPA). Compared to polypropylene glycol produced by the EO manufacturing method, polypropylene glycol produced by this bio-based fermentation method is preferred because it yields useful byproducts such as lactic acid from a safety perspective and also keeps manufacturing costs lower.

[0898] Butanediol derived from biomass can be produced by manufacturing diols from plant materials, fermenting them to obtain succinic acid, and then hydrogenating it.

[0899] Ethylene glycol derived from biomass can be produced, for example, from bioethanol obtained by conventional methods via ethylene.

[0900] As a polyfunctional alcohol derived from fossil fuels, compounds having two or more hydroxyl groups, preferably two to eight, per molecule can be used. Specifically, there are no particular limitations on the polyfunctional alcohol derived from fossil fuels; conventionally known substances can be used, such as, in addition to polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butanediol (BG), and hexamethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, trimethylolpropane, glycerol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, etc. These can be used alone or in combination of two or more.

[0901] As biomass-derived polyfunctional carboxylic acids, aliphatic polyfunctional carboxylic acids can be obtained from plant-based raw materials such as reproducible soybean oil, linseed oil, tung oil, coconut oil, palm oil, castor oil, etc., as well as recycled oils obtained from the recycling of waste edible oils mainly composed of these. Examples of biomass-derived aliphatic polyfunctional carboxylic acids include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acids. For example, sebacic acid is generated by the acid-base thermal decomposition of castor oil obtained from castor oil, with heptanol as a byproduct. In this invention, succinic acid or sebacic acid derived from biomass is particularly preferred. These can be used alone or in combination of two or more.

[0902] As polyfunctional carboxylic acids derived from fossil fuels, aliphatic or aromatic polyfunctional carboxylic acids can be used. For aliphatic polyfunctional carboxylic acids derived from fossil fuels, there are no particular limitations; conventionally known substances can be used, such as adipic acid, dodecanoic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acids, and their ester compounds. Similarly, for aromatic polyfunctional carboxylic acids derived from fossil fuels, there are no particular limitations; conventionally known substances can be used, such as isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, and their ester compounds. These can be used alone or in combination of two or more.

[0903] <Polyether polyols>

[0904] When a polyether polyol contains a component derived from biomass, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains a component derived from biomass. Examples of polyether polyols containing a component derived from biomass include the following.

[0905] • Reaction products of biomass-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates

[0906] • Reaction products of polyfunctional alcohols derived from fossil fuels and polyfunctional isocyanates derived from biomass

[0907] As polyfunctional alcohols derived from biomass and polyfunctional alcohols derived from fossil fuels, the polyfunctional alcohols derived from biomass and polyfunctional alcohols derived from fossil fuels described above in the section on polyester polyols can be used.

[0908] As a polyfunctional isocyanate derived from biomass, it can be obtained by amidation and reduction of a dicarboxylic acid from a plant to a terminal amino group, followed by reaction with phosgene to convert the amino group into an isocyanate group. Examples of biomass-derived polyfunctional isocyanates include biomass-derived diisocyanates. Examples of biomass-derived diisocyanates include dimer diisocyanate (DDI), octamethylene diisocyanate, and decamethylene diisocyanate. Alternatively, plant-derived diisocyanates can be obtained by using amino acids from plants as raw materials and converting the amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by esterifying the carboxyl methyl group of lysine to convert the amino group into an isocyanate group. Furthermore, 1,5-pentamethylene diisocyanate is obtained by decarboxylating the carboxyl group of lysine to convert the amino group into an isocyanate group.

[0909] Other methods for synthesizing 1,5-pentamethylene diisocyanate include phosgenation and carbamate esterification. More specifically, phosgenation involves reacting 1,5-pentamethylenediamine or its salt directly with phosgene, or suspending pentamethylenediamine hydrochloride in an inert solvent and reacting it with phosgene to synthesize 1,5-pentamethylenediisocyanate. Carbamate esterification involves first carbamateing 1,5-pentamethylenediamine or its salt to generate pentamethylenedicarbamate (PDC), and then synthesizing 1,5-pentamethylenediisocyanate through thermal decomposition. In this invention, a preferred polyisocyanate is the 1,5-pentamethylenediisocyanate-based polyisocyanate manufactured by Mitsui Chemicals Co., Ltd. (trade name: STABiO (registered trademark)).

[0910] As a polyfunctional isocyanate derived from fossil fuels, there are no particular limitations, and conventionally known substances can be used, such as: toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylenebis(phenylene isocyanate) (MDI), dextrin diisocyanate, benzyl diisocyanate, phenyl dimethyl diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-dibenzyl diisocyanate, and other aromatic diisocyanates. In addition, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate can be listed; alicyclic diisocyanates such as 1,4-cyclohexylene diisocyanate, 4,4-methylenebis(cyclohexyl)isocyanate, 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI can also be listed. These can be used alone or in combination of two or more.

[0911] <Polycarbonate polyols>

[0912] When polycarbonate polyols contain components derived from biomass, the reaction product of a polyfunctional alcohol containing components derived from biomass and a carbonate derived from fossil fuels can be used as the polycarbonate polyol. Alternatively, the reaction product of a polyfunctional alcohol containing components derived from fossil fuels and a carbonate derived from biomass can be used. Examples of carbonates include dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, and diphenyl carbonate. They can be used alone or in combination of two or more.

[0913] As a biomass-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol described in the above-mentioned polyester polyols can be used.

[0914] <Isocyanate compounds>

[0915] Next, the isocyanate compound will be described. As an isocyanate compound containing components derived from biomass, a biomass-derived polyfunctional isocyanate as described in the section on polyether polyols can be used.

[0916] Hydroxyl (meth)acrylate

[0917] Next, hydroxy methacrylates will be described. Examples of hydroxy methacrylates include: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and 2-hydroxy-3-phenoxypropyl methacrylate, which have one methacryloyl group; and hydroxy methacrylates with two or more methacryloyl groups, such as di(meth)acrylate, pentaerythritol tri(meth)acrylate, di(trimethylolpropane)tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and sorbitol penta(meth)acrylate. These can be used individually or in combination of two or more.

[0918] In addition to the aforementioned bio-carbamate (meth)acrylate, the adhesive resin of pattern layer 3 may also contain nitrocellulose. That is, pattern layer 3 may contain the aforementioned bio-carbamate (meth)acrylate, or it may contain nitrocellulose in addition to bio-carbamate (meth)acrylate.

[0919] Nitrocellulose

[0920] Nitrocellulose is a nitro-substituted cellulose resin formed by nitrifying a portion of the hydroxyl groups in the cellulose backbone. The cellulose backbone of nitrocellulose resin is a biomass material. As nitrocellulose, ordinary nitrocellulose can be used without hindrance, but nitrocellulose formed by replacing each glucose unit constituting the cellulose backbone with an average of 1.3 to 2.7 nitro groups is particularly preferred.

[0921] Nitrocellulose exists in L-form and H-form based on its molecular weight. Considering its solubility in organic solvents, the L-form is preferred.

[0922] The patterned layer 3 preferably has a biomass content of 5% or more, more preferably 5% or more and 50% or less, and even more preferably 10% or more and 50% or less. If the biomass content is within the above range, the amount of fossil fuel used can be reduced, thereby reducing the environmental impact. The dried weight of the patterned layer 3 is preferably 0.1 g / m³.2 ]Above 15 [g / m 2 The following, or more preferably, is 3 g / m 2 ]Above 10 [g / m 2 The following, and more preferably 6 g / m 2 Above 9 [g / m 2 The pattern layer 3 preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 0.5 μm or more and 5 μm or less, and even more preferably 0.7 μm or more and 3 μm or less. It should be noted that multiple pattern layers 3 having such weight or thickness may also be provided.

[0923] Regarding "biomass content", for example in the case of biocarbamate (meth)acrylate, as described above, it is determined as a value for the carbon content from biomass measured using radiocarbon (C14) determination.

[0924] Furthermore, regarding "biomass content," for example, in the case of nitrocellulose, since each glucose unit (formula = 172) constituting the cellulose backbone as the starting material contains 3 hydroxyl groups, 1 to 3 of these hydroxyl groups can undergo nitration (hydrogen is replaced by nitro groups (non-biomass material, formula = 46)). Thus, assuming the original cellulose backbone is composed of 100% by weight of biomass material, and with an average of n nitro groups being replaced per glucose unit, the proportion (by weight) of biomass material in the total nitrocellulose molecule can be calculated using (172-n) × 100 / (172-n + 46n).

[0925] Regarding the proportion of biomass material in the overall nitrocellulose molecule, it is approximately 78.8% by weight when each glucose unit constituting the cellulose backbone is replaced by an average of one nitro group, approximately 64.9% by weight when replaced by two nitro groups, and approximately 55.0% by weight when replaced by three nitro groups (calculated values ​​in the above formula).

[0926] Furthermore, when the thickness of the pattern layer 3 is less than 10 μm, the printability of the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.

[0927] In addition, to impart various functions, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesives, desiccants, curing agents, curing accelerators, and curing delayers can be added to pattern layer 3.

[0928] The pattern for pattern layer 3 can be any pattern, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, text, symbols, single-color pigments, or combinations thereof. Additionally, to improve the concealment of decorative piece 1, a concealing layer can be provided between pattern layer 3 and colored substrate layer 2. This concealing layer can be formed, for example, using opaque printing inks or coatings containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0929] Alternatively, the pattern layer 3 may be configured to have a solid-coated colored substrate layer to conceal the color / pattern of the base of the decorative piece 1, and a pattern layer for attaching a design-specific pattern.

[0930] <Adhesive Layer>

[0931] Adhesive layer 4 is stacked on one side of pattern layer 3 (in) Figure 1 On the top side (the middle side), there is a layer used to bond the pattern layer 3 and the transparent resin layer 5.

[0932] Materials used for adhesive layer 4 include, for example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, and polyolefin-based resins. In particular, considering adhesion to the transparent resin layer 5, polyolefin-based resins are preferred.

[0933] <Transparent resin layer>

[0934] The transparent resin layer 5 is stacked on one side of the adhesive layer 4 (in Figure 1 On the upper side (the middle side), there is a transparent resin layer formed of a resin composition containing the aforementioned polyethylene derived from biomass (from plants). More specifically, the transparent resin layer 5 is a resin layer formed of a resin composition containing polyethylene derived from biomass, which is polymerized from monomers containing ethylene derived from biomass. That is, in the transparent resin layer 5, a resin composition containing polyethylene derived from biomass used in the colored substrate layer 2 may also be used. In addition, it may contain polyethylene derived from fossil fuels, which is polymerized from monomers containing at least one of ethylene derived from fossil fuels and α-olefins, and ethylene derived from fossil fuels.

[0935] The transparent resin layer 5 may contain ethylene derived from biomass at a concentration of 5% or more by mass relative to the total amount of the transparent resin layer 5, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass. If the concentration of ethylene derived from biomass in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the past, and a carbon-neutral decorative sheet can be achieved.

[0936] The density of the transparent resin layer 5 is 0.92 g / cm³. 3Above 0.99 g / cm³ 3 Within the range below, preferably 0.94 g / cm³ 3 Above 0.98 g / cm³ 3 Within the range below, more preferably 0.95 g / cm³ 3 Above 0.97 g / cm³ 3 The density is within the range below. The density of the transparent resin layer 5 is determined by method A specified in JIS K7112-1980 after annealing as described in JIS K6760-1995. If the density of the transparent resin layer 5 is 0.92 g / cm³... 3 The above can improve the rigidity of the transparent resin layer 5. Additionally, if the density of the transparent resin layer 5 is 0.99 g / cm³, the rigidity can be increased. 3 The following steps can improve the transparency and mechanical strength of the transparent resin layer 5.

[0937] The transparent resin layer 5 has a thickness of 55-150 μm, preferably 55-100 μm, and more preferably 60-80 μm.

[0938] The transparent resin layer 5 may contain high-density polyethylene derived from biomass as the biomass-derived polyethylene.

[0939] In addition, the transparent resin layer 5 may contain polyethylene derived from biomass, which is a blend of high-density polyethylene from biomass and low-density polyethylene from biomass in the range of 100:0 to 20:80.

[0940] In addition, the overall biomass content of the transparent resin layer 5 can be in the range of 10% to 90%.

[0941] The manufacturing method of the transparent resin layer 5 is not particularly limited and can be manufactured by conventionally known methods. In the eighth embodiment, it is preferably formed by extrusion molding, and more preferably by T-die molding or blow molding.

[0942] In the eighth embodiment, the transparent resin layer 5 and the colored substrate layer 2 preferably satisfy the following specific relationships regarding density, thickness, and biomass density (ethylene concentration from biomass).

[0943] In the eighth embodiment, the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 preferably satisfy d2>d1. This is because formability is required for the transparent resin layer 5 to function, and productivity is required for the colored substrate layer 2 to function.

[0944] It should be noted that the ratio (d2 / d1) of the density d1 of the transparent resin layer 5 to the density d2 of the colored substrate layer 2 is preferably in the range of 1.1 to 1.5, more preferably in the range of 1.1 to 1.3, and even more preferably in the range of 1.1 to 1.2. By ensuring that the density ratio of the transparent resin layer to the colored substrate layer is within this range, even when using polyethylene derived from biomass, it can possess the extrusion suitability and bending processing suitability required for decorative sheets.

[0945] In the eighth embodiment, the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored substrate layer 2 preferably satisfy t1 ≥ t2. This is because a thickness is required for the transparent resin layer 5 to function, but a thickness similar to that of the transparent resin layer 5 is not required for the colored substrate layer 2 to function.

[0946] It should be noted that the ratio (t1 / t2) of the thickness t1 of the transparent resin layer 5 to the thickness t2 of the colored substrate layer 2 is preferably in the range of 1.1 to 3, more preferably in the range of 1.1 to 2, and even more preferably in the range of 1.1 to 1.5.

[0947] In the eighth embodiment, the ethylene concentration C1 from biomass in the transparent resin layer 5 and the ethylene concentration C2 from biomass in the colored substrate layer 2 preferably satisfy C1 > C2. This is because, since the transparent resin layer 5 is thick and uses a large amount of ethylene in order to function as a transparent resin layer 5, the amount of fossil fuel used can be further reduced by increasing the biomass content of the transparent resin layer 5.

[0948] Nucleating agents (e.g., "Rikemaster CN-002" manufactured by RichenVitamin Co., Ltd.) may also be added to the biomass-derived polyethylene that forms the transparent resin layer 5.

[0949] Based on the mass of polyethylene, the nucleating agent is preferably added to polyethylene in the range of 500 to 2000 ppm, and more preferably in the range of 1500 to 2000 ppm.

[0950] As needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers can be added to the transparent resin layer 5.

[0951] It should be noted that the transparent resin layer 5 preferably has a degree of transparency (colorless transparent, colored transparent, semi-transparent) that allows the pattern of the pattern layer 3 to be seen through the surface (top) of the decorative sheet 1.

[0952] It should be noted that in the eighth embodiment, polyethylene derived from biomass was described as the biomass-derived resin constituting the transparent resin layer 5, but the present invention is not limited thereto. For example, polypropylene or polybutene derived from biomass may be used instead of the aforementioned biomass-derived polyethylene. That is, in the eighth embodiment, polyolefins derived from biomass can be widely used as the biomass-derived resin constituting the transparent resin layer 5.

[0953] <Surface Protective Layer>

[0954] Surface protective layer 6 is stacked on one side of transparent resin layer 5 (in) Figure 1 The middle (upper side) is a layer designed to give decorative piece 1 functions such as weather resistance, damage resistance, stain resistance, and design.

[0955] The surface protective layer 6 can be formed using the same material as the adhesive resin of the pattern layer 3. Therefore, the structure of the surface protective layer 6 is the same as that of the pattern layer 3, except that it does not contain colorants.

[0956] The surface protective layer 6 is formed from a resin composition containing at least a polyol, an isocyanate compound, and a (meth)acrylate hydroxyl ester, namely, urethane (meth)acrylate or bio-urethane (meth)acrylate. Furthermore, in the surface protective layer 6, at least one of the polyol, isocyanate compound, or (meth)acrylate hydroxyl ester constituting the aforementioned urethane (meth)acrylate contains a component derived from biomass. That is, the surface protective layer 6 contains a component derived from biomass.

[0957] In addition to the adhesive resin of pattern layer 3, surface protective layer 6 may also contain nitrocellulose in addition to the aforementioned bio-urethane (meth)acrylate. That is, surface protective layer 6 may be formed from the aforementioned bio-urethane (meth)acrylate, or it may be formed by adding nitrocellulose to bio-urethane (meth)acrylate.

[0958] The surface protective layer 6 preferably has a biomass content of 5% or more, more preferably 5% or more and 50% or less, and even more preferably 10% or more and 50% or less. If the biomass content is within the above range, the amount of fossil fuel used can be reduced, thereby reducing the environmental impact. The dried weight of the surface protective layer 6 is preferably 0.1 g / m³. 2 ]Above 15 [g / m 2 The following, or more preferably, is 3 g / m 2 ]Above 10 [g / m 2 The following, and more preferably 6 g / m 2 Above 9 [g / m2 The surface protective layer 6 preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 3 μm or more and 10 μm or less, and even more preferably 6 μm or more and 9 μm or less.

[0959] In addition, depending on the requirements, the surface protective layer 6 may contain various additives such as weather resistant agents, plasticizers, stabilizers, fillers, dispersants, dyes, pigments and other colorants, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst trapping agents, colorants, light scattering agents, and gloss modifiers. Furthermore, depending on the requirements, the surface protective layer 6 may also contain functional additives such as antibacterial agents and antifungal agents.

[0960] <Concave and convex parts>

[0961] The uneven portion 7 is formed by recesses provided at multiple locations in the transparent resin layer 5 and the surface protective layer 6.

[0962] <Primer layer>

[0963] The primer layer 8 is a base layer used to improve the adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9.

[0964] In addition, the primer layer 8 is laminated on the other side of the colored substrate layer 2 (in Figure 1 (The middle is the lower side surface).

[0965] In addition, the primer layer 8 is formed, for example, using polyester resin, organic additives, pigments, etc.

[0966] It should be noted that, in order to improve corrosion resistance, anti-rust pigments can be added to the primer layer 8.

[0967] The thickness of the primer layer 8 is, for example, in the range of 1 [μm] to 10 [μm].

[0968] It should be noted that the above-described embodiments are an example of the present invention. The present invention is not limited to the above-described embodiments. Even in ways other than those described, as long as they do not depart from the technical concept of the present invention, various changes can be made according to the design, etc.

[0969] (Effects of the 8th embodiment)

[0970] If it is the decorative piece 1 of the eighth embodiment, it can achieve the effects described below.

[0971] (1) The colored substrate layer 2 and the transparent resin layer 5 are resin layers formed from a resin composition containing a biomass-derived polyolefin polymerized from monomers comprising olefins derived from biomass. The transparent resin layer 5 contains 5% by mass or more of the olefin derived from biomass and has a content of 0.92 g / cm³. 3 Above 0.99 g / cm³ 3 Within the following density range, the colored substrate layer 2 contains more than 5% by mass of olefins derived from biomass and has a density of 0.92 g / cm³. 3 The above is 1.12 g / cm³ 3 Within the following density range, pattern layer 3 contains colorants and components derived from biomass, and surface protective layer 6 contains components derived from biomass.

[0972] Therefore, it is possible to provide decorative sheets that can reduce the use of fossil fuels by using materials derived from plants, while maintaining physical properties suitable for use as decorative sheets.

[0973] (2) Pattern layer 3 is a resin layer containing a resin composition of at least polyol, isocyanate compound and (meth)acrylate hydroxy ester, namely urethane (meth)acrylate, and surface protective layer 6 is a resin layer formed by the urethane (meth)acrylate, wherein at least one of the polyol, isocyanate compound and (meth)acrylate hydroxy ester contained in the urethane (meth)acrylate contains a component derived from biomass.

[0974] Therefore, it is possible to provide decorative sheets that can reliably reduce the use of fossil fuels by using materials derived from plants, and reliably maintain physical properties suitable for use as decorative sheets.

[0975] (3) The polyols that constitute the bio-urethane (meth) acrylate contained in the pattern layer 3 and the surface protective layer 6 are polyester polyols containing components derived from biomass, polyether polyols containing components derived from biomass, or polycarbonate polyols containing components derived from biomass.

[0976] Therefore, it is possible to provide decorative sheets that can more reliably reduce the use of fossil fuels by using materials derived from plants, and can more reliably maintain the physical properties suitable for use as decorative sheets.

[0977] (4) The polyester polyols that are constituent elements of the above-mentioned bio-carbamate (meth)acrylates are either polyfunctional alcohols containing components from biomass and polyfunctional carboxylic acids containing components from fossil fuels, or polyfunctional alcohols containing components from fossil fuels and polyfunctional carboxylic acids containing components from biomass.

[0978] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0979] (5) The polyether polyols that are constituent elements of the above-mentioned bio-carbamate (meth)acrylates are reaction products of polyfunctional alcohols containing components from biomass and polyfunctional isocyanates containing components from fossil fuels, or reaction products of polyfunctional alcohols containing components from fossil fuels and polyfunctional isocyanates containing components from biomass.

[0980] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0981] (6) The polycarbonate polyols that are constituent elements of the above-mentioned bio-carbamate (meth)acrylates are either the reaction products of polyfunctional alcohols containing components from biomass and carbonates containing components from fossil fuels, or the reaction products of polyfunctional alcohols containing components from fossil fuels and carbonates containing components from biomass.

[0982] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0983] (7) The isocyanate compound that is a component of the bio-urethane (meth)acrylate contained in the pattern layer 3 and the surface protective layer 6 is an isocyanate compound containing components derived from biomass.

[0984] Thus, it is possible to provide decorative sheets that can further reliably reduce the use of fossil fuels by using materials derived from plants, and can further reliably maintain physical properties suitable for use as decorative sheets.

[0985] (8) A decorative sheet 1 having a substrate 9 and a decorative sheet 1 laminated on at least one side of the substrate 9.

[0986] Therefore, it is possible to provide decorative materials that can reduce the use of fossil fuels by using materials derived from plants, while maintaining physical properties suitable for use as decorative panels.

[0987] Example 6

[0988] Hereinafter, the decorative materials of Examples 1 to 16 and the decorative materials of Examples 1 to 3 will be described with reference to the 8th embodiment.

[0989] (Example 1)

[0990] After applying corona discharge treatment to one side of the substrate, a pattern layer, a urethane adhesive layer, a maleic anhydride modified polyethylene resin layer (transparent adhesive layer), a transparent resin layer, and a surface protective layer mainly composed of an acrylic resin composition are sequentially laminated on that side of the substrate. Furthermore, after applying corona discharge treatment to the other side of the substrate, a primer layer (thickness: 1-2 μm) composed of polyester urethane resin is formed. Thus, the decorative sheet of Example 1 (total thickness: 135 μm) is obtained.

[0991] In Example 1, a colored substrate layer (thickness: 55 μm) was used as the substrate, formed from a resin composition containing high-density polyethylene from biomass and low-density polyethylene from fossil fuels. The colored substrate layer was obtained by calendering this resin composition. The biomass content of the thus formed colored substrate layer was 80%, and the density of the colored substrate layer was 1.08 g / cm³. 3 ].

[0992] For the transparent resin layer, a transparent resin layer (thickness: 80 μm) is formed using a resin composition containing biomass-derived polyethylene (Braskem Corporation's "Biomass Polyethylene"). This biomass-derived polyethylene is a resin obtained by blending high-density polyethylene (SHC7260) and low-density polyethylene (SPB681) derived from biomass at a ratio (high-density polyethylene / low-density polyethylene) of 80 / 20. The transparent resin layer is obtained by extrusion lamination of this resin. The resulting transparent resin layer has a biomass content of 94% and a density of 0.95 g / cm³. 3 ].

[0993] The adhesive resin for the pattern layer uses a bio-urethane (meth)acrylate, a reaction product containing a polyester polyol derived from biomass, an isocyanate compound derived from fossil fuels, and a (meth)acrylate hydroxyl ester derived from fossil fuels. The polyester polyol containing the biomass component is a polyester polyol that is a reaction product of a polyfunctional alcohol containing the biomass component and a polyfunctional carboxylic acid derived from fossil fuels.

[0994] In addition, the surface protective layer is formed using the same bio-urethane (meth)acrylate as the adhesive resin of the pattern layer.

[0995] (Example 2)

[0996] As the polyester polyol in the bio-urethane (meth) acrylate that forms the surface protective layer, the decorative sheet of Example 2 was obtained by using the reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional carboxylic acid containing components derived from biomass, in the same manner as in Example 1.

[0997] (Example 3)

[0998] As the bio-urethane (meth)acrylate forming the surface protective layer, the bio-urethane (meth)acrylate is a reaction product of a polyester polyol derived from fossil fuels, an isocyanate compound containing components derived from biomass, and a (meth)acrylate hydroxyl ester derived from fossil fuels. Otherwise, the decorative sheet of Example 3 was obtained in the same manner as in Example 1.

[0999] (Example 4)

[1000] As the polyol in the bio-urethane (meth)acrylate that forms the surface protective layer, a polyether polyol was used, and otherwise, the decorative sheet of Example 4 was obtained in the same manner as in Example 1. Specifically, as the polyether polyol, the reaction product of a polyfunctional alcohol containing components from biomass and a polyfunctional isocyanate from fossil fuels was used.

[1001] (Example 5)

[1002] As the polyether polyol in the bio-urethane (meth) acrylate that forms the surface protective layer, the decorative sheet of Example 5 was obtained by using the reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional isocyanate containing components derived from biomass, in the same manner as in Example 4.

[1003] (Example 6)

[1004] The polyol used in the bio-urethane (meth)acrylate that forms the surface protective layer is a polyether polyol derived from fossil fuels. Otherwise, the decorative sheet of Example 6 was obtained in the same manner as in Example 3.

[1005] (Example 7)

[1006] As the polyol in the bio-urethane (meth)acrylate that forms the surface protective layer, a polycarbonate polyol was used. Otherwise, the decorative sheet of Example 7 was obtained in the same manner as in Example 1. Specifically, as the polycarbonate polyol, a reaction product of a polyfunctional alcohol containing components from biomass and a carbonate from fossil fuels was used.

[1007] (Example 8)

[1008] As the polyol in the bio-urethane (meth)acrylate that forms the surface protective layer, a polycarbonate polyol derived from fossil fuels was used. Otherwise, the decorative sheet of Example 8 was obtained in the same manner as in Example 3.

[1009] (Example 9)

[1010] The decorative sheet of Example 9 was obtained in the same manner as in Example 1, except that the polyester polyol in the bio-urethane (meth) acrylate, which is the adhesive resin of the pattern layer, was used as the reaction product of a polyfunctional alcohol from fossil fuels and a polyfunctional carboxylic acid containing components from biomass.

[1011] (Example 10)

[1012] The adhesive resin used as the pattern layer is bio-urethane (meth)acrylate. The reaction product of the bio-urethane (meth)acrylate, which is a polyester polyol derived from fossil fuels, an isocyanate compound containing components derived from biomass, and a (meth)acrylate hydroxyl ester derived from fossil fuels, was used. Otherwise, the decorative sheet of Example 10 was obtained in the same manner as in Example 1.

[1013] (Example 11)

[1014] The adhesive resin for the pattern layer is a polyol in bio-urethane (meth)acrylate, and a polyether polyol is used. Otherwise, the decorative sheet of Example 11 is obtained in the same manner as in Example 1. Specifically, the polyether polyol is a reaction product of a polyfunctional alcohol containing components from biomass and a polyfunctional isocyanate from fossil fuels.

[1015] (Example 12)

[1016] The decorative sheet of Example 12 was obtained in the same manner as in Example 11, except that the adhesive resin of the pattern layer was a polyether polyol in bio-urethane (meth) acrylate, which was a reaction product of a polyfunctional alcohol derived from fossil fuels and a polyfunctional isocyanate containing components derived from biomass.

[1017] (Example 13)

[1018] The adhesive resin used as the pattern layer is a polyol in bio-urethane (meth) acrylate, and a polyether polyol derived from fossil fuels is used. Otherwise, the decorative sheet of Example 13 is obtained in the same manner as in Example 10.

[1019] (Example 14)

[1020] The adhesive resin for the pattern layer is a polyol in bio-urethane (meth)acrylate, and a polycarbonate polyol is used. Otherwise, the decorative sheet of Example 14 is obtained in the same manner as in Example 1. Specifically, the polycarbonate polyol is a reaction product of a polyfunctional alcohol containing components from biomass and a carbonate from fossil fuels.

[1021] (Example 15)

[1022] The adhesive resin used as the pattern layer is a polyol in bio-urethane (meth) acrylate, and a polycarbonate polyol derived from fossil fuels is used. Otherwise, the decorative sheet of Example 15 is obtained in the same manner as in Example 10.

[1023] (Example 16)

[1024] High-density polyethylene (SHC7260) from biomass and low-density polyethylene (SPB681) from biomass were blended in a ratio (high-density polyethylene / low-density polyethylene) of 100 / 0. A transparent resin layer was obtained by extruding and laminating the resin. Otherwise, the decorative sheet of Example 16 was obtained in the same manner as in Example 1.

[1025] (See Example 1 for reference)

[1026] A pattern layer was formed from urethane-based printing ink, and a surface protective layer was formed from acrylic-based UV-curable resin. Otherwise, the decorative sheet of Reference Example 1 was obtained in the same manner as in Example 1.

[1027] (See Example 2 for reference)

[1028] Except that a transparent resin layer was obtained by extruding and laminating homopolymer polypropylene resin derived from fossil fuels produced by Prime Polymer Co., Ltd., the decorative sheet of Reference Example 2 was obtained in the same manner as in Example 1.

[1029] (See Example 3 for reference)

[1030] Except that the colored substrate layer was obtained using only colored polyethylene resin derived from fossil fuels, the decorative sheet of Reference Example 3 was obtained in the same manner as in Example 1.

[1031] (Performance evaluation, evaluation results)

[1032] For the decorative sheets of Examples 1 to 16 and the decorative sheets of Reference Examples 1 to 3, the following were evaluated: “haze of transparent resin layer (%)”, “pencil hardness”, “Hoffman scratch test”, “extrusion suitability”, and “bending whitening”. The following methods were used as the evaluation methods.

[1033] <Haze of the transparent resin layer (%)>

[1034] Using an ultraviolet-visible-near infrared spectrophotometer (manufacturer: Shimadzu Corporation, model: UV-3600), the haze (%) of the transparent resin layer was measured.

[1035] Resin having the same composition as the transparent resin layer of each example / reference example was extruded within the range of a thickness of 70 [μm] or more and 80 [μm] or less to obtain a resin film. The haze at a wavelength of 555 nm was measured using a spectrophotometer (integrating sphere), and the haze was evaluated. Then, a case where the haze was less than 15% was evaluated as "◎", a case where the haze was 15% or more and less than 25% was evaluated as "○", and a case where the haze was 25% or more was evaluated as "×".

[1036] It should be noted that in this example, "◎" and "○" were set as qualified.

[1037] <Pencil hardness>

[1038] The pencil hardness was measured using a pencil hardness testing machine (automatic) (manufacturer: Yoshimitsu Seiki Co., Ltd., model: C221A).

[1039] After performing a pencil hardness test on the decorative material including the decorative sheet of each example / reference example using pencils with different hardnesses, the damage (depression) generated on the surface (surface protective layer) was confirmed, and the surface hardness was evaluated. Then, a case where damage occurred on the surface after performing a pencil hardness test using a pencil with a hardness of 2B or more was evaluated as "◎", and a case where damage occurred on the surface after performing a pencil hardness test using a pencil with a hardness of 4B or more was evaluated as "○". In addition, a case where damage occurred on the surface after performing a pencil hardness test using a pencil with a hardness of 5B or less was evaluated as "×".

[1040] It should be noted that in this example, "◎" and "○" were set as qualified.

[1041] <Hoffman scratch test>

[1042] The Hoffman scratch test was performed as follows: A scratching blade (a cylindrical blade with a diameter of Φ7) was set to contact the surface of the decorative sheet at an angle of 45 degrees, and the testing machine was moved on the decorative sheet.

[1043] Scratches were generated by gradually increasing the load (heavy object) within the range of 200 to 2000 g (increments of 200 g each), and the load (g) at which damage occurred on the surface of the sample was evaluated. It should be noted that in the case where damage occurred at a load of 800 g, "600 g" was recorded as the tolerance load in the table.

[1044] It should be noted that in this example, a case where the tolerance load was "200 g" was set as unqualified.

[1045] <Extrusion adaptability>

[1046] The transparent resin layer was extruded to confirm its production suitability (extrusion suitability).

[1047] As a result, if the product can be manufactured (formed) without any problems, it is marked as "0" (qualified). On the other hand, situations where defects may occur are marked as "△" (unqualified).

[1048] <Bending Whitening>

[1049] Use the decorative sheet (i.e., decorative material) pasted on the MDF to confirm the suitability of V-cut processing (whether there is bending whitening).

[1050] As a result, cases without whitening were marked as "○" (pass), cases with slight whitening were marked as "△" (pass), and cases with whitening were marked as "×" (fail).

[1051]

[1052]

[1053]

[1054] The results of evaluating various properties using the above methods show that the decorative sheets of Examples 1 to 16 exhibited superior performance, equivalent to or better than that of Reference Examples 1-3, in all evaluation tests. That is, it can be seen that the decorative sheets of Examples 1 to 16, by using materials derived from plants, can reduce the use of fossil fuels and maintain physical properties suitable for use as decorative sheets.

[1055] (9th implementation)

[1056] The following is for reference Figure 1 The composition of decorative material 10 is explained.

[1057] like Figure 1 As shown, the decorative material 10 comprises a decorative piece 1 and a substrate 9. It should be noted that the specific composition of the decorative piece 1 will be described later.

[1058] It should be noted that the composition of the decorative material 10 in the 9th embodiment is the same as that in the 1st embodiment, except for the composition of the decorative piece 1. Therefore, the description of the composition other than the decorative piece 1 is omitted.

[1059] (Composition of decorative pieces)

[1060] like Figure 1As shown, the decorative piece 1 has a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface protective layer 6, a raised and recessed portion 7, and a primer layer 8.

[1061] <Colored substrate layer>

[1062] The colored substrate layer 2 is a resin layer formed using thermoplastic resin. It is a colored resin layer formed from a resin composition containing polyethylene derived from biomass (from plants). Furthermore, the colored resin layer contains inorganic substances.

[1063] The composition of the colored substrate layer 2 will be described in detail below.

[1064] (Polyethylene derived from biomass)

[1065] In the ninth embodiment, the polyethylene derived from biomass is polymerized from monomers containing ethylene derived from biomass. There is no particular limitation on the ethylene derived from biomass; ethylene produced by conventionally known methods can be used. Since ethylene derived from biomass is used as the monomer source, the polymerized polyethylene is derived from biomass.

[1066] It should be noted that the raw material monomers of polyethylene may not contain 100% by mass ethylene derived from biomass.

[1067] The monomers used as raw materials for polyethylene derived from biomass may further contain at least one of ethylene derived from fossil fuels and α-olefins derived from fossil fuels, and may further contain α-olefins derived from biomass.

[1068] There is no particular limitation on the number of carbon atoms in the aforementioned α-olefins; α-olefins with 3 to 20 carbon atoms are generally used, with butene, hexene, or octene being preferred. This is because butene, hexene, or octene can be manufactured by polymerizing ethylene, which is a feedstock derived from biomass. Furthermore, by containing such α-olefins, the polymerized polyethylene has an alkyl group as a branched structure, thus making it more flexible than simple linear polyethylene.

[1069] By using ethylene as a feedstock from biomass, it is theoretically possible to produce it from 100% biomass components.

[1070] The ethylene concentration from biomass in the aforementioned polyethylene (hereinafter sometimes referred to as "biomass content") is a value obtained by measuring the carbon content from biomass using radiocarbon (C14) determination. It is known that atmospheric carbon dioxide contains a certain proportion (105.5 pMC) of C14; therefore, the C14 content in plants that absorb atmospheric carbon dioxide (e.g., corn) is also approximately 105.5 pMC. Furthermore, it is known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in polyethylene, the proportion of carbon from biomass can be calculated. In the 9th embodiment, the carbon content from biomass, Pbio, when the C14 content in polyethylene is set to PC14, can be calculated as follows.

[1071] Pbio(%)=P C14 / 105.5×100

[1072] In the ninth embodiment, theoretically, if all ethylene from biomass is used as the raw material for polyethylene, the concentration of ethylene from biomass is 100%, and the biomass degree of the polyethylene from biomass is 100. Furthermore, in fossil fuel polyethylene manufactured solely from fossil fuel raw materials, the concentration of ethylene from biomass is 0%, and the biomass degree of the polyethylene from fossil fuels is 0.

[1073] In the ninth embodiment, the polyethylene derived from biomass or the decorative sheet containing such polyethylene does not require a biomass content of 100.

[1074] In the ninth embodiment, the polymerization method for monomers containing ethylene derived from biomass is not particularly limited, and can be carried out using conventionally known methods. The polymerization temperature and polymerization pressure can be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and conventionally known apparatus can be used. Hereinafter, an example of a polymerization method for monomers containing ethylene will be described.

[1075] The polymerization method for ethylene polymers or copolymers of ethylene and α-olefins can be appropriately selected based on the type of target polyethylene, such as the density or branching of high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). For example, it is preferable to use multi-site catalysts such as Ziegler-Natta catalysts or single-site catalysts such as metallocene catalysts as polymerization catalysts, and to carry out the polymerization in one or more stages using any of the following methods: gas-phase polymerization, slurry polymerization, solution polymerization, and high-pressure ionic polymerization.

[1076] In addition, polyethylene derived from biomass can be a polymer of ethylene alone or a copolymer of ethylene and α-olefins, or a mixture of two or more.

[1077] (A resin composition containing polyethylene derived from biomass)

[1078] In the ninth embodiment, the resin composition contains the aforementioned polyethylene as a main component. The resin composition contains at least 5% by mass, preferably 5 to 95% by mass, and more preferably 25 to 75% by mass of ethylene derived from biomass relative to the total resin composition. If the concentration of ethylene derived from biomass in the resin composition is 5% by mass or more, the amount of fossil fuel used can be reduced compared to conventional methods, enabling the achievement of carbon-neutral decorative sheets.

[1079] The above-mentioned resin composition may contain two or more types of polyethylene with different biomass concentrations, as long as the concentration of ethylene from biomass as a whole is within the above-mentioned range.

[1080] The resin composition described above may further comprise polyethylene derived from fossil fuels, which is obtained by polymerizing a monomer comprising at least one of ethylene and α-olefins derived from fossil fuels, and ethylene derived from fossil fuels. That is, in embodiment 9, the resin composition may also be a mixture of polyethylene derived from biomass and polyethylene derived from fossil fuels. The mixing method is not particularly limited, and conventionally known methods can be used. For example, dry blending or melt blending may be employed.

[1081] According to the ninth embodiment, the resin composition contains 5% by mass or more, preferably 5 to 90% by mass, and more preferably 25 to 75% by mass of polyethylene derived from biomass. The resin composition may contain a mixture of polyethylene derived from biomass and, for example, polyethylene derived from fossil fuels. Even when using a resin composition containing such a mixture, as long as the concentration of ethylene derived from biomass is 5% by mass or more, preferably 5 to 90% by mass, and more preferably 25 to 75% by mass, the resin composition as a whole is acceptable.

[1082] In the resin composition manufactured in the above-described resin composition manufacturing process, various additives may be added in addition to polyethylene as the main component, without impairing its properties. Examples of additives include plasticizers, UV stabilizers, anti-staining agents, matting agents, deodorizers, flame retardants, weathering agents, antistatic agents, yarn friction reducers, slip agents, anti-sticking agents, antioxidants, ion exchangers, and coloring pigments. These additives are preferably added in the range of 1 to 20% by mass, more preferably 1 to 10% by mass, relative to the total resin composition.

[1083] (Inorganic matter)

[1084] The colored substrate layer 2 contains inorganic substances, and the specific gravity of the colored substrate layer 2 is above 0.97 and below 1.5.

[1085] As an inorganic material, one or more of the following can be used: calcium carbonate, titanium dioxide, carbon black, silicon dioxide, chromium, antimony, titanium complexes and other oxides.

[1086] As described above, the coloring substrate layer 2 contains 5% by mass or more ethylene from biomass relative to the total coloring substrate layer 2. If the concentration of ethylene from biomass in the coloring substrate layer 2 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the past, and carbon-neutral decorative sheets can be achieved.

[1087] Furthermore, inorganic materials are added to the colored substrate layer 2 in such a way that the specific gravity is between 0.97 and 1.5. By adding inorganic materials to the colored substrate layer 2 in such a way that the specific gravity is between 0.97 and 1.5, the concealment of the colored substrate layer 2 can be improved.

[1088] In the colored substrate layer 2, the polyethylene derived from biomass can be any of the following: polyethylene containing high-density polyethylene and low-density polyethylene derived from biomass; polyethylene containing high-density polyethylene derived from biomass and low-density polyethylene derived from fossil fuels; polyethylene containing high-density polyethylene derived from fossil fuels and low-density polyethylene derived from biomass. In addition, the overall biomass content of the colored substrate layer 2 can be in the range of 10% to 90%.

[1089] It should be noted that high-density polyethylene derived from biomass refers to polyethylene with a density exceeding 0.94. Conversely, low-density polyethylene derived from biomass refers to polyethylene with a density below 0.94.

[1090] In the colored substrate layer 2, the polyethylene derived from biomass can be a blend of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) (which can be derived from either biomass or fossil fuels) in a ratio ranging from 95:5 to 70:30. When the content of LDPE is low, the film-forming stability is poor; when the content of LDPE is high, the film becomes too soft.

[1091] The manufacturing method of the colored substrate layer 2 is not particularly limited and can be manufactured by conventionally known methods. In the ninth embodiment, it is preferably formed by calendering.

[1092] Additionally, as needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers may be added to the colored substrate layer 2.

[1093] The thickness of the colored substrate layer 2 is preferably in the range of 40 μm to 200 μm, more preferably 51 μm to 200 μm, and even more preferably 55 μm to 100 μm. This is because when the thickness of the colored substrate layer 2 is 40 μm or more, it can absorb unevenness and steps in the flooring material or the like used as the base, thereby allowing for a good installation of the decorative sheet 1. Furthermore, when the thickness of the colored substrate layer 2 is 200 μm or less, a colored substrate layer 2 exceeding the required thickness will not be formed, thereby reducing the manufacturing cost of the decorative sheet 1.

[1094] It should be noted that in the ninth embodiment, polyethylene derived from biomass was described as the resin constituting the coloring substrate layer 2, but the present invention is not limited thereto. For example, polypropylene or polybutene derived from biomass may be used instead of the aforementioned polyethylene derived from biomass. That is, in the ninth embodiment, polyolefins derived from biomass can be widely used as the resin constituting the coloring substrate layer 2.

[1095] <Pattern Layer>

[1096] Pattern layer 3 is stacked on one side of colored substrate layer 2 (in) Figure 1 On the top side (the middle side), there is a layer for attaching patterns to give the design. It should be noted that if the coloring of the base material layer 2 can be used instead, the pattern layer 3 can also be omitted.

[1097] In addition, the pattern layer 3 is formed using printing inks or coatings. The printing inks or coatings that form the pattern layer 3 are formed, for example, by dissolving or dispersing colorants such as dyes or pigments together with a suitable binder resin in a suitable diluent.

[1098] The printing inks or coatings that form the pattern layer 3 are applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roller coating.

[1099] As an adhesive resin, for example, urethane resins, acrylic resins, vinyl chloroacetate resins, polyimide resins, nitrocellulose, or mixtures thereof can be used, but are not limited thereto.

[1100] As the pattern, any pattern can be used, such as wood grain, stone grain, fabric grain, abstract patterns, geometric patterns, text, symbols, single-color pigments, or combinations thereof. Furthermore, to improve the concealment of the decorative piece 1, a concealing layer can be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer can be formed, for example, using opaque printing inks or coatings containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[1101] The thickness of the pattern layer 3 is preferably in the range of 1 μm to 10 μm. This is because when the thickness of the pattern layer 3 is 1 μm or more, the printing becomes clearer. In addition, when the thickness of the pattern layer 3 is 10 μm or less, the printability of the decorative sheet 1 is improved, and manufacturing costs can be reduced.

[1102] In addition, to impart various functions, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesives, desiccants, curing agents, curing accelerators, and curing delayers can be added to pattern layer 3.

[1103] Alternatively, the pattern layer 3 may be configured to have a solid-coated colored substrate layer to conceal the color / pattern of the base of the decorative piece 1, and a pattern layer for attaching a design-specific pattern.

[1104] <Adhesive Layer>

[1105] Adhesive layer 4 is stacked on one side of pattern layer 3 (in) Figure 1 On the top side (the middle side), there is a layer used to bond the pattern layer 3 and the transparent resin layer 5.

[1106] Materials used for adhesive layer 4 include, for example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, and polyolefin-based resins. In particular, considering adhesion to the transparent resin layer 5, polyolefin-based resins are preferred.

[1107] <Transparent resin layer>

[1108] The transparent resin layer 5 is stacked on one side of the adhesive layer 4 (in Figure 1On the upper side (the middle side), there is a transparent resin layer formed of a resin composition containing polyethylene derived from biomass (from plants) or a resin composition containing polyethylene derived from fossil fuels. More specifically, the transparent resin layer 5 is a resin layer formed of a resin composition containing polyethylene derived from biomass, which is polymerized from monomers containing ethylene derived from biomass. That is, for the transparent resin layer 5, a resin composition containing polyethylene derived from biomass used in the coloring substrate layer 2 without the addition of inorganic substances can be used. In other words, both the coloring substrate layer 2 and the transparent resin layer 5 are formed of a resin composition containing polyethylene derived from biomass (from plants), with inorganic substances further added to the coloring substrate layer 2, but no inorganic substances added to the transparent resin layer 5. Since no inorganic material is added to the transparent resin layer 5 located above the pattern layer 3, but only to the colored substrate layer 2 located below the pattern layer 3, the pattern layer 3 is suppressed from being hidden by maintaining the transparency of the transparent resin layer 5, while improving the concealment of the colored substrate layer 2, thereby concealing the color / pattern of the substrate to which the decorative piece 1 is pasted.

[1109] The transparent resin layer 5 may contain ethylene derived from biomass at a concentration of 5% or more by mass relative to the total amount of the transparent resin layer 5, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, and most preferably 40 to 75% by mass. If the concentration of ethylene derived from biomass in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the past, and a carbon-neutral decorative sheet can be achieved.

[1110] The transparent resin layer 5 may contain high-density polyethylene derived from biomass as the biomass-derived polyethylene.

[1111] In addition, the transparent resin layer 5 may contain polyethylene derived from biomass, which is a blend of high-density polyethylene from biomass and low-density polyethylene from biomass in the range of 100:0 to 20:80.

[1112] In addition, the overall biomass content of the transparent resin layer 5 can be in the range of 10% to 90%.

[1113] The manufacturing method of the transparent resin layer 5 is not particularly limited and can be manufactured by conventionally known methods. In the ninth embodiment, it is preferably formed by extrusion molding, and more preferably by T-die molding or blow molding.

[1114] A nucleating agent (such as “Rikemaster CN-002” manufactured by RickenVitamin Co., Ltd.) can be added to the biomass-derived polyethylene that forms the transparent resin layer 5.

[1115] Based on the mass of polyethylene, the nucleating agent is preferably added to polyethylene in the range of 500 to 2000 ppm, and more preferably in the range of 1500 to 2000 ppm.

[1116] As needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers can be added to the transparent resin layer 5.

[1117] It should be noted that the transparent resin layer 5 preferably has a degree of transparency (colorless transparent, colored transparent, semi-transparent) that allows the pattern of the pattern layer 3 to be seen through the surface (top) of the decorative sheet 1.

[1118] <Surface Protective Layer>

[1119] Surface protective layer 6 is stacked on one side of transparent resin layer 5 (in) Figure 1 The middle (upper side) is a layer designed to give decorative piece 1 functions such as weather resistance, damage resistance, stain resistance, and design.

[1120] In addition, the surface protective layer 6 is formed, for example, using an acrylic resin composition.

[1121] In addition, depending on the requirements, the surface protective layer 6 may contain various additives such as weather resistant agents, plasticizers, stabilizers, fillers, dispersants, dyes, pigments and other colorants, solvents, ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst trapping agents, colorants, light scattering agents, and gloss modifiers. Furthermore, depending on the requirements, the surface protective layer 6 may also contain functional additives such as antibacterial agents and antifungal agents.

[1122] <Concave and convex parts>

[1123] The uneven portion 7 is formed by recesses provided at multiple locations in the transparent resin layer 5 and the surface protective layer 6.

[1124] <Primer layer>

[1125] The primer layer 8 is a base layer used to improve the adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9.

[1126] In addition, the primer layer 8 is laminated on the other side of the colored substrate layer 2 (in Figure 1 (The middle is the lower side surface).

[1127] In addition, the primer layer 8 is formed, for example, using polyester resin, organic additives, pigments, etc.

[1128] It should be noted that, in order to improve corrosion resistance, anti-rust pigments can be added to the primer layer 8.

[1129] The thickness of the primer layer 8 is, for example, in the range of 1 [μm] to 10 [μm].

[1130] <Concentration of ethylene from biomass in decorative panels>

[1131] As described above, the colored substrate layer 2 and the transparent resin layer 5 each contain 5% by mass or more of ethylene from biomass, and the decorative sheet 1 as a whole preferably contains 5% by mass or more of materials from biomass.

[1132] <Overall proportion of decorative panels>

[1133] By adding inorganic materials to the colored thermoplastic resin layer, the overall specific gravity of the decorative sheet 1 is preferably 0.97 to 1.5 or less. This allows, for example, the formation of a decorative sheet 1 with a level of concealment comparable to that formed using polyethylene derived from fossil fuels.

[1134] It should be noted that the above-described embodiments are an example of the present invention. The present invention is not limited to the above-described embodiments. Even in ways other than those described, as long as they do not depart from the technical concept of the present invention, various changes can be made according to the design, etc.

[1135] (Effects of the 9th embodiment)

[1136] If it is the decorative piece 1 of the 9th embodiment, it can achieve the following effects.

[1137] (1) The colored substrate layer 2 is a resin layer formed by a resin composition containing ethylene from biomass, containing 5% by mass or more of ethylene from biomass, and inorganic matter is added to the colored substrate layer 2, and the specific gravity of the colored substrate layer 2 is 0.97 or more and 1.5 or less.

[1138] Therefore, even when using materials derived from plants, i.e., polyethylene derived from biomass, a colored substrate layer 2 can be formed that has the same level of concealment as a composition formed using polyethylene derived from fossil fuels.

[1139] As a result, even when using plant-derived materials, i.e., polyethylene formed from biomass, decorative panels 1 can be provided that can suppress the reduction of concealment.

[1140] (2) At least one of the transparent resin layer 5 and the colored substrate layer 2 may contain high-density polyethylene from biomass and low-density polyethylene from biomass as the polyethylene from biomass.

[1141] As a result, a transparent resin layer 5 and a colored substrate layer 2 that are further made more flexible can be formed.

[1142] (3) The transparent resin layer 5 may contain polyethylene derived from biomass, which is a blend of high-density polyethylene derived from biomass and low-density polyethylene derived from biomass in the range of 100:0 to 20:80.

[1143] As a result, a transparent resin layer 5 with high hardness can be formed.

[1144] (4) The colored substrate layer 2 may contain high-density polyethylene and low-density polyethylene derived from biomass as the polyethylene derived from biomass, and the biomass content may be in the range of 10% to 90%.

[1145] As a result, a colored substrate layer 2 with good film-forming stability and sufficient flexibility as a decorative sheet can be formed.

[1146] Furthermore, if the decorative material 10 of the 9th embodiment is used, the following effects can be achieved.

[1147] (5) Having a substrate 9 and a decorative sheet 1 laminated on at least one side of the substrate 9.

[1148] As a result, even when using plant-derived materials, i.e., polyethylene formed from biomass, decorative materials 10 can be provided that can suppress the reduction of concealment.

[1149] Example 7

[1150] Hereinafter, the decorative sheets of Examples 1 to 6 and the decorative sheets of Comparative Examples 1 to 3 will be described with reference to the 9th embodiment.

[1151] (Example 1)

[1152] After applying corona discharge treatment to one side of the substrate, a pattern layer printed with urethane-based printing ink, a urethane-based adhesive layer, a maleic anhydride-modified polyethylene resin layer (adhesive layer), a transparent resin layer, and a surface protective layer mainly composed of an acrylic resin composition are sequentially layered on that side of the substrate. Furthermore, after applying corona discharge treatment to the other side of the substrate, a primer layer (thickness: 1-2 μm) composed of polyester urethane resin is formed on that other side of the substrate. Thus, the decorative sheet of Example 1 (total thickness: 135 μm) is obtained. The biomass content of the decorative sheet is 80%.

[1153] A decorative material can be obtained by bonding MDF (Medium Density Fiberboard) to the primer layer side of the decorative sheet using adhesives such as BA-10L manufactured by Japan Coating Resin Corporation and curing agent BA-11B manufactured by Japan Coating Resin Corporation.

[1154] In Example 1, a colored substrate layer (thickness: 55 μm) was used as the substrate, formed from a resin composition containing biomass-derived polyethylene (“Green Polyethylene” manufactured by Braskem Corporation) and with added inorganic materials. The biomass-derived polyethylene was a resin blended from high-density polyethylene and low-density polyethylene derived from biomass. Calcium carbonate and titanium oxide were added as inorganic materials to achieve a specific gravity of 1.2 for the colored substrate layer. The colored substrate layer was obtained by extrusion lamination of this resin. The biomass content of the thus formed colored substrate layer was 80%.

[1155] The transparent resin layer, similar to the colored substrate layer, is a transparent resin layer (thickness: 60 μm) formed from a resin composition containing biomass-derived polyethylene ("Green Polyethylene" manufactured by Braskem Corporation), but without the addition of inorganic substances. This biomass-derived polyethylene is a resin obtained by blending high-density polyethylene (SHC7260) and low-density polyethylene (SPB681) from biomass at a ratio of 80 / 20 (high-density polyethylene / low-density polyethylene). The transparent resin layer is obtained by extrusion lamination of this resin.

[1156] (Example 2)

[1157] Except that calcium carbonate was used as an inorganic material to make the specific gravity of the colored substrate layer 0.97, the decorative sheet of Example 2 was obtained in the same manner as in Example 1.

[1158] (Example 3)

[1159] Except that calcium carbonate and titanium oxide were used as inorganic materials in such a way as to make the specific gravity of the colored substrate layer 1.5, the decorative sheet of Example 3 was obtained in the same manner as in Example 1.

[1160] (Example 4)

[1161] Except that calcium carbonate and titanium oxide were used as inorganic materials in a manner that made the specific gravity of the colored substrate layer 1.0, the decorative sheet of Example 4 was obtained in the same manner as in Example 1.

[1162] (Example 5)

[1163] Except that a transparent resin layer was formed using polypropylene derived from fossil fuels, the decorative sheet of Example 5 was obtained in the same manner as in Example 1.

[1164] (Example 6)

[1165] High-density polyethylene (SHC7260) from biomass and low-density polyethylene (SPB681) from biomass were blended in a ratio (high-density polyethylene / low-density polyethylene) of 100 / 0, and the resin was extruded and laminated to obtain a transparent resin layer. Otherwise, the decorative sheet of Example 6 was obtained in the same manner as in Example 1.

[1166] (Comparative Example 1)

[1167] Except that calcium carbonate and titanium oxide were combined as inorganic materials in such a way as to make the specific gravity 0.96, the decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1.

[1168] (Comparative Example 2)

[1169] Except that titanium oxide was used as an inorganic material to achieve a specific gravity of 0.95, the decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1.

[1170] (Comparative Example 3)

[1171] Except that calcium carbonate and titanium oxide were combined as inorganic materials in such a way as to make the specific gravity 1.6, the decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1.

[1172] (Performance evaluation, evaluation results)

[1173] The decorative sheets of Examples 1 to 5 and the decorative sheets of Comparative Examples 1 to 3 were evaluated for "concealment", "productivity of the colored thermoplastic resin layer (colored substrate layer)" and "p...

Claims

1. A decorative sheet comprising a colored substrate layer and a transparent thermoplastic resin layer laminated on one side of the colored substrate layer, The colored substrate layer contains polyolefin derived from biomass, with a content of 0.92 g / cm³. 3 The above 1.12g / cm 3 Density within the following range.

2. The decorative piece according to claim 1, wherein, The transparent thermoplastic resin layer has a content of 0.92 g / cm³. 3 Above 0.99g / cm 3 Density within the following range.

3. The decorative piece according to claim 1, wherein, When the thickness of the transparent thermoplastic resin layer is set to t1 and the thickness of the colored substrate layer is set to t2, the condition is that t2≤t1 and t1 / t2 is within the range of 1.1 to 3.

4. The decorative piece according to claim 1, wherein, When the density of the transparent thermoplastic resin layer is set to d1 and the density of the colored substrate layer is set to d2, d2>d1 is satisfied.

5. The decorative piece according to claim 1, wherein, The colored substrate layer and the transparent thermoplastic resin layer are resin layers formed from a resin composition containing a biomass-derived polyolefin polymerized from monomers comprising olefins derived from biomass.

6. The decorative piece according to claim 1, wherein, At least one of the transparent thermoplastic resin layer and the colored substrate layer contains high-density polyethylene and low-density polyethylene derived from biomass as the biomass-derived polyolefin.

7. The decorative piece according to claim 5 or claim 6, wherein, The transparent thermoplastic resin layer contains polyethylene as the biomass-derived polyolefin, which is a blend of high-density polyethylene and low-density polyethylene derived from biomass in the range of 100:0 to 20:

80.

8. The decorative piece according to claim 1, wherein, The colored substrate layer contains high-density polyethylene and low-density polyethylene derived from biomass as the polyolefin derived from biomass, and the biomass content is in the range of 10% to 90%.

9. A decorative material, comprising: Substrate, and The decorative sheet of any one of claims 1 to 8 is laminated on at least one side of the substrate.

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